Propylene copolymer, polypropylene composition and uses thereof, transition metal compound and olefin polymerization catalyst

ABSTRACT

A transition metal compound represented by the following formula (2a):

CROSS-REFERENCE TO RELATED APPLICATIONS

The present application is a 37 CFR §1.53(b) divisional of U.S.application Ser. No. 10/550,017 filed Jun. 29, 2006, which claimspriority on PCT International Application No. PCT/JP03/16972 filed Dec.26, 2003, which in turn claims priority on Japanese Application No.2003-090161 filed Mar. 28, 2003. Each of these applications is herebyincorporated by reference.

FIELD OF THE INVENTION

The present invention relates to a propylene/1-butene random copolymer,a propylene elastomer, a polypropylene composition containing thepropylene/1-butene random copolymer, a sheet, a film and an orientedfilm comprising the polypropylene composition, and a polypropylenecomposite film that includes a layer comprising the polypropylenecomposition.

The present invention is also relates to a transition metal compoundthat has a novel and specific structure effective as a component forolefin polymerization catalyst, and an olefin polymerization catalystcontaining the transition metal compound.

Further, the present invention relates to a polyolefin resincomposition, and more particularly to a polyolefin resin compositioncomprising a specific propylene polymer and a specific elastomer.

BACKGROUND OF THE INVENTION

Polypropylenes are versatile thermoplastic molding materials withexcellent properties, including high stiffness, heat resistance andtransparency. On the other hand, the flexibility and impact resistanceof polypropylenes are inadequate so that they are generally incorporatedwith soft rubber components. Although incorporation of soft rubbercomponents compensates for the insufficient flexibility and impactresistance of polypropylenes, the resultant polypropylene compositionshave lowered heat resistance. Further, such polypropylene compositionsare required to have improved low-temperature heat-sealability.

Accordingly, there has been a demand for a polypropylene compositionthat has excellent flexibility and impact resistance as well assufficient heat resistance and low-temperature heat-sealability.

Meanwhile, crystalline polypropylenes have excellent mechanicalproperties including tensile strength, stiffness, surface hardness andimpact strength; optical properties including gloss and transparency;and food sanitation properties including nontoxicity and odorlessness.These properties provide wide applications particularly for foodpackaging purposes. However, single layer films consisting of thecrystalline polypropylenes shrink at heat seal temperatures so thatdifficulties are caused in heat sealing such films. Therefore, thecrystalline polypropylene films are generally combined with aheat-sealing layer that comprises a polymer such as a low-densitypolyethylene or a propylene/ethylene random copolymer.

The heat-sealing layers made from such polymers are required:

(1) to be heat-sealable at considerably lower temperatures than are thesubstrate films (crystalline polypropylene films);

(2) to have high heat-sealing strength of little deterioration withtime;

(3) to have good adhesion to the substrate films;

(4) to be as transparent as or more transparent than the substratefilms;

(5) to cause no blocking during storage;

(6) not to adhere to bag-making machines or jigs of filling andpackaging machinery; and

(7) to have superior scratch resistance.

However, traditional heat-sealing materials do not satisfy all theseproperties. For example, low-density polyethylene films, althoughheat-sealable at low temperatures, have poor heat-sealing strength, badadhesion to the substrate films and low transparency, and are alsoliable to adhere to packaging jigs.

Propylene/ethylene random copolymers can meet the above properties (2)to (7) but fail to satisfy the property (1). Therefore, thepolypropylene composite films that include a heat-sealing layercomprising a propylene/ethylene random copolymer have a narrow range ofheat-seal temperatures. Accordingly, heat sealing of these compositefilms by automatic packaging or bag-making machines requires strictcontrol of the heat seal temperatures. Other materials proposed so farfor the heat-sealing materials include blends of the propylene/ethylenerandom copolymers with ethylene/α-olefin copolymers. Such blends haveimproved low-temperature heat-sealability relative to thepropylene/ethylene random copolymers, but their transparency isinferior.

The present applicant has found that a propylene/1-butene randomcopolymer which contains 55 to 85 wt % propylene and has a crystallineheat of fusion between 20 and 80 J/g as measured on a differentialscanning calorimeter, is effectively used as a heat-sealing materialbecause of its high transparency and excellent low-temperatureheat-sealability. The present applicant has proposed a heat-sealinglayer for polypropylene films that is formed from a composition whichcomprises the propylene/1-butene random copolymer in an amount of 50 wt% or more and an isotactic polypropylene (JP-A-S54-114887). Theheat-sealing layer comprising the above composition has excellentlow-temperature heat-sealability and blocking resistance, but is ratherinferior in blocking and scratch resistances to the heat-sealing layersfrom the propylene/ethylene random copolymers. The present applicant hasalso proposed a composite film with excellent heat-sealability(JP-B-S61-42626); the composite film comprises an isotacticpolypropylene film and a heat-sealing layer that comprises a compositioncontaining the propylene/1-butene copolymer in an amount of 10 to 40 wt% and a crystalline propylene/α-olefin random copolymer.

Moreover, these polypropylene films need further improvements to meetthe demand for higher-speed packaging. For example, excellent slipproperties and blocking resistance as well as enhanced low-temperatureheat-sealability are required.

JP-A-H08-238733 discloses a composite film that includes a heat-sealinglayer comprising a metallocene-catalyzed propylene/1-butene copolymerand a crystalline propylene/α-olefin random copolymer. This referencehas a problem that when the propylene/1-butene copolymer has a meltingpoint of around 70° C., crystallization rate is lowered to cause badproductivity. Also, the moldability and the appearance of the film aremore deteriorated when the propylene/1-butene copolymer has a largeamount.

Metallocene compounds are of much interest recently as homogenouscatalysts for olefin polymerization. Olefin polymerization with use ofthe metallocene compounds, particularly stereoregular polymerization ofα-olefins, has been studied by many since the report of isotacticpolymerization by W. Kaminsky, et al. (Angew. Chem. Int. Ed. Engl., 24,507 (1985)).

In α-olefin polymerization using the metallocene compounds, it has beenfound that the stereoregularity and the molecular weights of resultantα-olefin polymers are widely varied by use of the compounds in which asubstituent group is introduced into a cyclopentadienyl ring of a ligandor in which two cyclopentadienyl rings are bridged.

For example, propylene polymerization in the presence of a metallocenecompound having a ligand in which a cyclopentadienyl ring and afluorenyl ring are bridged, will yield stereoregular polymers such as:

syndiotactic polypropylenes when the polymerization is catalyzed bydimethylmethylene(cyclopentadienyl)(fluorenyl)zirconium dichloride (J.Am. Chem. Soc., 110, 6255 (1988));

hemiisotactic polypropylenes under catalysis by the above compound withintroduction of a methyl group into the third position of thecyclopentadienyl ring, i.e., under catalysis bydimethylmethylene(3-methylcyclopentadienyl)(fluorenyl)zirconiumdichloride (JP-A-H03-193796); and

isotactic polypropylenes under catalysis by the above compound withintroduction of a tert-butyl group into the third position of thecyclopentadienyl ring, i.e., under catalysis bydimethylmethylene(3-tert-butylcyclopentadienyl)(fluorenyl)zirconiumdichloride (JP-A-H06-122718). Further,dimethylmethylene(3-tert-butyl-5-methylcyclopentadienyl)(fluorenyl)zirconiumdichloride can catalyze polymerization of propylene to provide higherisotacticity when tert-butyl groups are introduced into the third andsixth positions of the fluorenyl ring (i.e.,dimethylmethylene(3-tert-butyl-5-methylcyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirconiumdichloride) (WO01/27124).

With respect to the influence on the molecular weights:

dimethylmethylene(cyclopentadienyl)(fluorenyl)zirconium dichloride canproduce syndiotactic polypropylenes having higher molecular weights whenthe bridging group between the cyclopentadienyl ring and fluorenyl ringis altered to a diphenylmethylene group (i.e.,diphenylmethylene(cyclopentadienyl)(fluorenyl)zirconium dichloride)(JP-A-H02-274703);

dimethylmethylene(3-(2-adamantyl)-cyclopentadienyl)(fluorenyl)zirconiumdichloride can produce isotactic-hemiisotactic polypropylenes havinghigher molecular weights when the bridging group is altered to adiphenylmethylene group (i.e.,diphenylmethylene(3-(2-adamantyl)-cyclopentadienyl)(fluorenyl)zirconiumdichloride) (Organometallics, 21, 934 (2002)); and

dimethylmethylene(3-tert-butylcyclopentadienyl)(fluorenyl)zirconiumdichloride can produce isotactic polypropylenes having higher molecularweights when a methyl group is introduced into the fifth position of thecyclopentadienyl ring (i.e.,dimethylmethylene(3-tert-butyl-5-methylcyclopentadienyl)(fluorenyl)zirconiumdichloride) (JP-A-2001-526730).

Contrary, polypropylenes with lower molecular weights result whensubstituent groups are introduced into two adjacent positions in thecyclopentadienyl ring of a catalyst component (JP-A-2001-526730 andJP-A-H10-226694); for example,dimethylmethylene(3-tert-butyl-2-methylcyclopentadienyl)(fluorenyl)zirconiumdichloride anddiphenylmethylene(3,4-dimethylcyclopentadienyl)(fluorenyl)zirconiumdichloride can catalyze polymerization so as to give lower molecularweight polypropylenes relative todimethylmethylene(3-tert-butyl-5-methylcyclopentadienyl)(fluorenyl)zirconiumdichloride anddiphenylmethylene(3-methylcyclopentadienyl)(fluorenyl)zirconiumdichloride, respectively.

Meanwhile, synthesis of metallocene compounds that have a ligand inwhich a cyclopentadienyl group with substituent groups at twonon-adjacent positions (e.g. third and fifth positions) and a fluorenylgroup are bridged via an (alkyl)(aryl)methylene group or adiarylmethylene group, has been unsuccessful. This is attributed to thetroublesome preparation of such ligand by the established method due todifficult reaction between a fluorene metal salt and a6,6-diphenylfulvene derivative whose five-membered ring is substitutedwith such as an electron-donating hydrocarbon group. Furthermore, suchselective introduction of substituent groups into two non-adjacentpositions is difficult with the method disclosed in JP-A-H10-226694.

In general, the polymerization catalysts containing the metallocenecompounds are required for further improvements in terms ofpolymerization activity, stereoregularity and molecular weight control.In particular, a polymerization catalyst that contains a metallocenecompound as described in JP-A-H10-298221 can copolymerize ethylene andpropylene while avoiding fouling, but the resultant copolymer has aremarkably lower molecular weight than a propylene homopolymer obtainedwith the catalyst.

Also, a polymerization catalyst that contains a metallocene compound asdescribed in JP-A-H10-120733 copolymerizes ethylene and propylene toprovide a higher molecular weight copolymer with no fouling. However,since this polymerization catalyst essentially requires a specificcombination of an ionic compound and a metallocene compound, itsversatility is rather limited.

As described above, olefin polymerization, for example copolymerizationof ethylene and propylene, with these catalysts containing themetallocene compounds, has been almost unable to produce polymers havinghigh molecular weights.

The present invention aims at solving the aforesaid problems. Thepresent inventors have developed a novel transition metal compounduseful as an olefin polymerization catalyst component that has a ligandin which a cyclopentadienyl ring with substituent groups at twonon-adjacent positions and a fluorenyl ring are bridged via anaryl-substituted carbon atom, and also an olefin polymerization catalystcontaining the transition metal compound. The present invention has beenaccomplished based on these findings.

Polyolefin resins, such as propylene block copolymers, have manyapplications including daily necessities, kitchenware, packaging films,home electric appliances, machine parts, electrical parts and automobileparts. These products and parts are mainly manufactured by injectionmolding due to high productivity. When resin compositions that containpropylene block copolymers are injection molded, circular ripples,called flow marks or tiger marks, occur on molded articles in thecross-flow direction. Noticeable flow marks on surfaces deteriorate theappearance of the molded articles so that they are concealed by paintingor the like according to need. To cover up or obscure the flow marks onthe molded articles obtained from the resin compositions containingpropylene block copolymers, the resin compositions are injected into ahigh-temperature mold. However, this process requires a special mold andalso the molding cycle is prolonged, causing productivity problems.

On the other hand, JP-A-H10-1573 discloses a composition comprising ametallocene-catalyzed propylene block copolymer and an α-olefincopolymer rubber. The metallocene-catalyzed propylene block copolymershave low crystallinity due to an approximate 1% of occurrence of1,3-insertion or 2,1-insertion of propylene monomer. As a result, theirmelting points fall around 150° C., while propylene block copolymersprepared using titanium catalysts have melting points of 160° C. orseveral degrees higher. Further, the metallocene-catalyzed propyleneblock copolymers have lower tensile strength and flexural strengthproperties and stiffness than propylene block copolymers prepared withuse of titanium catalysts. Therefore, practical use of the compositionscomprising the metallocene-catalyzed propylene block copolymers andα-olefin copolymer rubbers has been unrealized due to their inferiormechanical strength properties to the compositions comprisingtitanium-catalyzed propylene block copolymers and α-olefin copolymerrubbers.

DISCLOSURE OF THE INVENTION

The present invention has objects of providing a propylene/1-butenerandom copolymer that has excellent flexibility, impact resistance, heatresistance and low-temperature heat-sealability, a polypropylenecomposition comprising the propylene/1-butene random copolymer, and apolypropylene composite film that can be obtained with good moldabilityand has superior transparency, low-temperature heat-sealability,blocking resistance and mechanical strength such as scratch resistance.

The propylene/1-butene random copolymer (PBR) according to the presentinvention has:

(1) a content of propylene-derived units of 60 to 90 mol % and a contentof 1-butene-derived units of 10 to 40 mol %;

(2) a triad isotacticity of 85 to 97.5% as determined from a ¹³C-NMRspectrum;

(3) a molecular weight distribution (Mw/Mn) of 1 to 3 as measured by gelpermeation chromatography (GPC);

(4) an intrinsic viscosity of 0.1 to 12 dl/g as measured in decalin at135° C.;

(5) a melting point (Tm) of 40 to 120° C. as measured on a differentialscanning calorimeter; and

(6) a relation between the melting point (Tm) and the content (M) of1-butene constituent units (mol %) of:146 exp(−0.022M)≧Tm≧125 exp(−0.032M).

The polypropylene composition (CC-1) according to the inventioncomprises 5 to 95 wt % of a polypropylene (PP-A) and 95 to 5 wt % of apropylene/1-butene random copolymer (PBR), the propylene/1-butene randomcopolymer (PBR) having:

(1) a content of propylene-derived units of 60 to 90 mol % and a contentof 1-butene-derived units of 10 to 40 mol %;

(2) a triad isotacticity of 85 to 97.5% as determined from a ¹³C-NMRspectrum;

(3) a molecular weight distribution (Mw/Mn) of 1 to 3 as measured by gelpermeation chromatography (GPC);

(4) an intrinsic viscosity of 0.1 to 12 dl/g as measured in decalin at135° C.;

(5) a melting point (Tm) of 40 to 120° C. as measured on a differentialscanning calorimeter; and

(6) a relation between the melting point (Tm) and the content (M) of1-butene constituent units (mol %) of:146 exp(−0.022M)≧Tm≧125 exp(−0.032M).

The polypropylene composite film according to the present inventioncomprises a crystalline polypropylene layer (I) and a polypropylenecomposition layer (II) disposed on at least one surface of thecrystalline polypropylene layer (I), the polypropylene composition layer(II) comprising a polypropylene composition (CC-2) that comprises 0 to95 wt % of a crystalline polypropylene (PP-A) and 5 to 100 wt % of apropylene/1-butene random copolymer (PBR), the propylene/1-butene randomcopolymer (PBR) having:

(1) a content of propylene-derived units of 60 to 90 mol % and a contentof 1-butene-derived units of 10 to 40 mol %;

(2) a triad isotacticity of 85 to 97.5% as determined from a ¹³C-NMRspectrum;

(3) a molecular weight distribution (Mw/Mn) of 1 to 3 as measured by gelpermeation chromatography (GPC);

(4) an intrinsic viscosity of 0.1 to 12 dl/g as measured in decalin at135° C.;

(5) a melting point (Tm) of 40 to 120° C. as measured on a differentialscanning calorimeter; and

(6) a relation between the melting point (Tm) and the content (M) of1-butene constituent units (mol %) of:146 exp(−0.022M)≧Tm≧125 exp(−0.032M).

The propylene/1-butene random copolymer (PBR) is preferably obtained bycopolymerizing propylene and 1-butene in the presence of an olefinpolymerization catalyst that comprises:

(1a) a transition metal compound,

(1b) an organoaluminum oxy-compound, and/or

(2b) a compound capable of forming an ion pair by reacting with thetransition metal compound (1a), and optionally

(c) an organoaluminum compound; the transition metal compound (1a)having the formula (1a):

wherein R³ is a hydrocarbon group or a silicon-containing group; R¹, R²and R⁴, which may be the same or different, are each a hydrogen atom, ahydrocarbon group or a silicon-containing group; R⁵, R⁶, R⁷, R⁸, R⁹,R¹⁰, R¹¹, R¹², R¹³ and R¹⁴ which may be the same or different, are eacha hydrogen atom, a hydrocarbon group or a silicon-containing group;neighboring substituent groups of R⁵ to R¹² may link together to form aring; R¹³ and R¹⁴, which may be the same or different, may link togetherto form a ring; M denotes a Group-4 transition metal; Y denotes a carbonatom; Q denotes a halogen atom, a hydrocarbon group, an anionic ligandor a neutral ligand capable of coordination by a lone pair of electrons,and may be the same or different when plural; and j is an integer of 1to 4.

The sheet or film according to the present invention comprises thepolypropylene composition.

The oriented film of the present invention is obtained by orienting thesheet, film or composite film in at least one direction.

The propylene elastomer (PBER) according to the present inventioncontains (1):

(a) propylene-derived units in an amount of 50 to 85 mol %,

(b) 1-butene-derived units in an amount of 5 to 25 mol %, and

(c) ethylene-derived units in an amount of 10 to 25 mol %, with thepropylene-derived units and the ethylene-derived units having a molarratio of 89/11 to 70/30 (propylene content/ethylene content); and

has a modules in tension (YM) of 40 MPa or less as measured inaccordance with JIS 6301.

The propylene elastomer (PBER) is preferably obtained by copolymerizingpropylene, ethylene and 1-butene in the presence of an olefinpolymerization catalyst that comprises:

(1a) a transition metal compound,

(1b) an organoaluminum oxy-compound, and/or

(2b) a compound capable of forming an ion pair by reacting with thetransition metal compound (1a), and optionally

(c) an organoaluminum compound; the transition metal compound (1a)having the formula (1a):

wherein R³ is a hydrocarbon group or a silicon-containing group; R¹, R²and R⁴, which may be the same or different, are each a hydrogen atom, ahydrocarbon group or a silicon-containing group; R⁵, R⁶, R⁷, R⁸, R⁹,R¹⁰, R¹¹, R¹², R¹³ and R¹⁴, which may be the same or different, are eacha hydrogen atom, a hydrocarbon group or a silicon-containing group;neighboring substituent groups of R⁵ to R¹² may link together to form aring; R¹³ and R¹⁴, which may be the same or different, may link togetherto form a ring; M denotes a Group-4 transition metal; Y denotes a carbonatom; Q denotes a halogen atom, a hydrocarbon group, an anionic ligandor a neutral ligand capable of coordination by a lone pair of electrons,and may be the same or different when plural; and j is an integer of 1to 4.

The present invention has other objects of providing a novel transitionmetal compound useful as an olefin polymerization catalyst component, anolefin polymerization catalyst that contains the transition metalcompound, and a process for producing high molecular weight olefinpolymers.

The transition metal compound according to the present invention isrepresented by the formula (2a):

wherein R¹ and R³ are each a hydrogen atom; R² and R⁴, which may be thesame or different, are each a hydrocarbon group or a silicon-containinggroup; R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹² and R¹³, which may be the sameor different, are each a hydrogen atom, a hydrocarbon group or asilicon-containing group; neighboring substituent groups of R⁵ to R¹²may link together to form a ring; R¹⁴ is an aryl group; R¹³ and R¹⁴,which may be the same or different, may link together to form a ring; Mdenotes a Group-4 transition metal; Y denotes a carbon atom; Q denotes ahalogen atom, a hydrocarbon group, an anionic ligand or a neutral ligandcapable of coordination by a lone pair of electrons, and may be the sameor different when plural; and j is an integer of 1 to 4.

The transition metal compound (3a) according to the present inventionhas the formula (2a) in which both R¹³ and R¹⁴ are aryl groups.

The olefin polymerization catalyst according to the present inventioncomprises (A) the transition metal compound (2a) or (3a) and (B) atleast one compound selected from:

(B-1) an organometallic compound,

(B-2) an organoaluminum oxy-compound, and

(B-3) a compound capable of forming an ion pair by reacting with thetransition metal compound (A).

The process for producing olefin polymers according to the presentinvention comprises polymerizing one or more monomers selected fromethylene and α-olefins in the presence of the olefin polymerizationcatalyst, wherein at least one monomer is ethylene or propylene.

In the process for producing olefin polymers, the transition metalcompound (2a) or (3a) is preferably used in a supported form on acarrier.

The olefin polymerization catalyst containing the aforesaid transitionmetal compound can polymerize one or more monomers selected fromethylene and α-olefins to yield olefin copolymers having remarkably highmolecular weights. The one or more monomers essentially contain at leasteither ethylene or propylene.

In consideration of the above-mentioned background art, the presentinvention has further objects of providing a polyolefin resincomposition that comprises a specific propylene polymer and a specificelastomer, and uses of the polyolefin resin composition.

The polyolefin resin composition according to the present inventioncomprises a propylene polymer (PP-C) and at least one elastomer selectedfrom metallocene-catalyzed elastomers (EL-1) to (EL-4) and contains theelastomer(s) in an amount of 10 parts by weight or more based on 100parts by weight of the propylene polymer (PP-C); wherein:

the elastomer (EL-1) is a propylene/ethylene random copolymer that has:

I) contents of propylene-derived constituent units and ofethylene-derived constituent units in a molar ratio of 80/20 to 20/80;

II) an intrinsic viscosity [η] of 1.5 dl/g or more;

III) a ratio (Mw/Mn) of 1.0 to 3.5 in terms of a weight-averagemolecular weight (Mw) to a number-average molecular weight (Mn) asmeasured by gel permeation chromatography (GPC); and

IV) a ratio of 1.0 mol % or less in terms of irregularly bondedpropylene monomers based on 2,1-insertion to all the propyleneconstituent units as determined from a ¹³C-NMR spectrum;

the elastomer (EL-2) is a random copolymer of ethylene and an α-olefinof 4 to 20 carbon atoms that has:

I) contents of ethylene-derived constituent units and ofα-olefin-derived constituent units in a molar ratio of 80/20 to 20/80;

II) an intrinsic viscosity [η] of 1.5 dl/g or more;

III) a ratio (Mw/Mn) of 1.0 to 3.5 in terms of a weight-averagemolecular weight (Mw) to a number-average molecular weight (Mn) asmeasured by gel permeation chromatography (GPC); and

IV) a ratio of 1.0 mol % or less in terms of irregularly bonded α-olefinmonomers based on 2,1-insertion to all the α-olefin constituent units asdetermined from a ¹³C-NMR spectrum;

the elastomer (EL-3) is a random copolymer of propylene and an α-olefinof 4 to 20 carbon atoms that has:

I) contents of propylene-derived constituent units and ofα-olefin-derived constituent units in a molar ratio of 80/20 to 20/80;

II) an intrinsic viscosity [η] of 1.5 dl/g or more;

III) a ratio (Mw/Mn) of 1.0 to 3.5 in terms of a weight-averagemolecular weight (Mw) to a number-average molecular weight (Mn) asmeasured by gel permeation chromatography (GPC);

IV) a ratio of 1.0 mol % or less in terms of irregularly bondedpropylene monomers based on 2,1-insertion to all the propyleneconstituent units as determined from a ¹³C-NMR spectrum; and

V) a melting point (Tm) of not more than 150° C. or outside themeasurable range according to DSC measurement;

the elastomer (EL-4) is a random copolymer of ethylene, propylene and anα-olefin of 4 to 20 carbon atoms that has:

I) contents of ethylene-derived constituent units and ofpropylene-derived constituent units in a molar ratio of 80/20 to 20/80;

II) contents of ethylene-derived and propylene-derived constituent units(EP), and of C₄₋₂₀ α-olefin-derived constituent units (OL) in a molarratio of 99/1 to 20/80 ((EP)/(OL));

III) an intrinsic viscosity [η] of 1.5 dl/g or more;

IV) a ratio (Mw/Mn) of 1.0 to 3.5 in terms of a weight-average molecularweight (Mw) to a number-average molecular weight (Mn) as measured by gelpermeation chromatography (GPC); and

V) a ratio of 1.0 mol % or less in terms of irregularly bonded propylenemonomers based on 2,1-insertion to all the propylene constituent units,and a ratio of 1.0 mol % or less in terms of irregularly bonded α-olefinmonomers based on 2,1-insertion to all the α-olefin constituent units asdetermined from a ¹³C-NMR spectrum; and

the metallocene catalyst comprises:

(1a) a transition metal compound,

(1b) an organoaluminum oxy-compound, and/or

(2b) a compound capable of forming an ion pair by reacting with thetransition metal compound (1a), and optionally

(c) an organoaluminum compound; the transition metal compound (1a)having the formula (1a):

wherein R³ is a hydrocarbon group or a silicon-containing group; R¹, R²and R⁴, which may be the same or different, are each a hydrogen atom, ahydrocarbon group or a silicon-containing group; R⁵, R⁶, R⁷, R⁸, R⁹,R¹⁰, R¹¹, R¹², R¹³ and R¹⁴ which may be the same or different, are eacha hydrogen atom, a hydrocarbon group or a silicon-containing group;neighboring substituent groups of R⁵ to R¹² may link together to form aring; R¹³ and R¹⁴, which may be the same or different, may link togetherto form a ring; M denotes a Group-4 transition metal; Y denotes a carbonatom; Q denotes a halogen atom, a hydrocarbon group, an anionic ligandor a neutral ligand capable of coordination by a lone pair of electrons,and may be the same or different when plural; and j is an integer of 1to 4.

The elastomers (EL-1) to (EL-4) of the present invention are preferablyobtained by polymerization at 40° C. or above.

The polyolefin resin composition may contain the elastomers (EL-1) to(EL-4) in an amount of 20 parts by weight or more based on 100 parts byweight of the propylene polymer (PP-C).

The propylene polymer (PP-C) in the polyolefin resin composition may bea propylene homopolymer or a random copolymer of propylene and ethyleneor an α-olefin of 4 to 20 carbon atoms that has:

I) a melting point (Tm) of 140° C. or above as measured by DSC; and

II) a melt flow rate (MFR) of 0.01 to 1000 g/10 min as measured at 230°C. under a load of 2.16 kg.

The propylene polymer (PP-C) in the polyolefin resin composition may bea propylene homopolymer or a random copolymer of propylene and ethyleneand/or an α-olefin of 4 to 20 carbon atoms that has a ratio (Mw/Mn) of1.0 to 4.0 in terms of a weight-average molecular weight (Mw) to anumber-average molecular weight (Mn) as measured by gel permeationchromatography (GPC).

The propylene polymer (PP-C) in the polyolefin resin composition may beprepared using a magnesium-supported titanium catalyst.

The propylene polymer (PP-C) in the polyolefin resin composition may beprepared using a metallocene catalyst.

The propylene polymer (PP-C) in the polyolefin resin composition maycomprise a polymer portion (A1) prepared mainly using a catalyst systemof titanium tetrachloride supported on magnesium chloride, and a polymerportion (A2) prepared using a metallocene catalyst, with the polymerportions (A1) and (A2) having a weight ratio of 1/99 to 99/1((A1)/(A2)).

The propylene polymer portion (A2) in the polyolefin resin compositionmay have a ratio of 0.2 mol % or less in terms of irregularly bondedpropylene monomers based on 2,1-insertion or 1,3-insertion to all thepropylene constituent units as determined from a ¹³C-NMR spectrum.

The polyolefin resin composition may be obtained by producing thepropylene polymer (PP-C) and successively producing the elastomers(EL-1) to (EL-4).

The polyolefin resin composition may also be obtained by producing apropylene polymer portion (PP-C2) with a metallocene catalyst andsuccessively producing the elastomers (EL-1) to (EL-4), and adding apropylene polymer portion (PP-C1) obtained mainly with a catalyst systemof titanium tetrachloride supported on magnesium chloride.

The polyolefin resin composition may also be obtained by mixing thepropylene polymer portion (PP-C1) and the elastomers (EL-1) to (EL-4)produced as described above.

Uses of the polyolefin resin composition include injection moldedarticles for general purposes, injection molded articles for use asautomobile parts, parts of home electric appliances, containers andmedical apparatus parts, hollow vessels, films, sheets and fibers.

BRIEF DESCRIPTION OF THE DRAWING

FIG. 1 is a schematic cross-sectional view of the unoriented sheetprepared in Example 1b.

PREFERRED EMBODIMENTS OF THE INVENTION

Hereinbelow, the polypropylene composition according to the presentinvention will be described in detail. The polypropylene compositioncomprises a polypropylene described below and a specificpropylene/1-butene copolymer.

The polypropylene (PP-A) for use in the present invention may beselected from numerous conventional polypropylenes. The polypropylenemay be a homopolypropylene or a propylene random copolymer that containsa small amount, for example 10 mol % or less, preferably less than 5 mol%, of units derived from an olefin other than the propylene. In thepresent invention, the propylene random copolymer is preferably used.

The other olefins for the propylene random copolymer include α-olefinsof 2 to 20 carbon atoms other than the propylene, such as ethylene,1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene,1-dodecene, 1-hexadecene and 4-methyl-1-pentene.

For use in the present invention, polypropylenes produced by theconventional process using a known solid titanium catalyst component aresuitable. Metallocene-catalyzed polypropylenes may also be favorablyused.

The polypropylene (PP-A) of the present invention desirably has amelting point (Tm) of 100 to 165° C., preferably 120 to 165° C. Thepolypropylene desirably has a melting point which is within the aboverange and is higher than that of a later-described propylene/1-butenerandom copolymer (PBR) when incorporated to the polypropylenecomposition. The melting point (TmA) of the polypropylene (PP-A) ishigher than the melting point (TmB) of the propylene/1-butene randomcopolymer (PBR) by 10 to 100° C., preferably by 20 to 90° C.

The polypropylene (PP-A) desirably has a melt flow rate (MFR) (ASTMD1238, 230° C., 2.16 kg load) generally of 0.1 to 400 g/10 min,preferably 0.5 to 100 g/10 min, and has a molecular weight distribution(Mw/Mn) of above 3, desirably from 4 to 15.

The polypropylene (PP-A) generally has a hardness higher than that ofthe propylene/1-butene random copolymer (PBR).

The polypropylene composite film according to the invention includes asubstrate layer (1) that is formed from a crystalline polypropylene(PP-B). The crystalline polypropylene of the present invention may beselected from those polypropylenes commonly used for films. Preferably,the crystalline polypropylene (PP-B) has an isotactic index (I.I.)(content of boiling n-heptane insolubles) of 75% or more, preferablyfrom 75 to 99%, a density of 0.89 to 0.92 g/cm³, and a melt index(otherwise a melt flow rate) at 230° C. of 0.1 to 10 dg/min. Althoughthe crystalline polypropylene used herein is generally ahomopolypropylene, a propylene random copolymer that contains a smallamount, for example 5 mol % or less, of units derived from an olefinother than the propylene may be used without adversely affecting theobjects of the present invention. The olefins include α-olefins of 2 to20 carbon atoms other than the propylene, such as ethylene, 1-butene,1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-dodecene,1-hexadecene and 4-methyl-1-pentene. The crystalline polypropylene(PP-B) for use in the present invention may be obtained by theconventional process using a known solid titanium catalyst component ora metallocene catalyst component. The crystalline polypropylene (PP-B)may optionally contain additives, including heat stabilizers,ultraviolet light absorbers, anti-blocking agents, slip agents andantistatic agents.

In the present invention, the polypropylene (PP-B) may be selected froma number of known polypropylenes for forming the crystallinepolypropylene layer. The polypropylene may be a homopolypropylene or apropylene random copolymer that contains a small amount, for example 10mol % or less, preferably less than 5 mol %, of units derived from anolefin other than the propylene. The homopolypropylene may be preferablyused in the present invention due to its high stiffness.

The propylene/1-butene random copolymer (PBR) contains propylene-derivedunits in an amount of 60 to 90 mol %, preferably 65 to 88 mol %, morepreferably 70 to 85 mol %, and still more preferably 70 to 75 mol %, and1-butene-derived units in an amount of 10 to 40 mol %, preferably 12 to35 mol %, more preferably 15 to 30 mol %, and still more preferably 25to 30 mol %. When the propylene/1-butene random copolymer of the presentinvention has a melting point of 75° C. or below, its crystallizationrate (½ crystallization time) at 45° C. is 10 minutes or less,preferably 7 minutes or less.

The propylene/1-butene random copolymer (PBR) may contain additionalconstituent units derived from an olefin other than the propylene andthe 1-butene, for example ethylene-derived constituent units, in anamount of 10 mol % or less. (2) Stereoregularity (triad tacticity, mmfraction) of propylene/1-butene random copolymer (PBR)

The stereoregularity of the propylene/1-butene copolymer (PBR) can beevaluated based on the triad tacticity (mm fraction).

The mm fraction is defined as a proportion of methyl groups branched inthe same direction in a triad sequence of propylene units that arehead-to-tail bonded to form a zigzag structure. The mm fraction isdetermined from a ¹³C-NMR spectrum as described below.

Determination of the mm fraction of the propylene/1-butene randomcopolymer (PBR) from a ¹³C-NMR spectrum involves investigation of peaksassigned to (i) a triad sequence of propylene units that arehead-to-tail bonded and (ii) a triad sequence of propylene and buteneunits that are head-to-tail bonded with a propylene unit in the middle(the second unit).

The mm fraction is obtained from peak intensities assigned to side-chainmethyl groups in the second units (propylene units) of the triadsequences (i) and (ii). Details are as follows.

An NMR sample is prepared in a sample tube by completely dissolving thepropylene/1-butene random copolymer (PBR) in a lock solvent consistingof hexachlorobutadiene and a small amount of deuterated benzene, and the¹³C-NMR spectrum of the resultant sample is recorded with completeproton decoupling at 120° C. Measurement conditions are such that theflip angle is 45° and the pulse intervals are at least 3.4 Tl (Tl is thelongest spin-lattice relaxation time for the methyl group). Themethylene and methine groups have shorter Tl than the methyl group, sothat all the carbons in the sample will have a magnetization recoveryrate of 99% or more under the above conditions. The chemical shift isbased on tetramethylsilane as the standard: the peak assigned to themethyl group carbon of the third unit in a pentad sequence (mmmm) ofhead-to-tail bonded propylene units is set to 21.593 ppm, and otherpeaks of carbon are determined relative to that peak.

With respect to the ¹³C-NMR spectrum of the propylene/1-butene randomcopolymer (PBR) recorded as above, the carbons in the side-chain methylgroups of the propylene units give peaks in an approximate range of 19.5to 21.9 ppm: the first peak range about 21.0 to 21.9 ppm, the secondpeak range about 20.2 to 21.0 ppm and the third peak range about 19.5 to20.2 ppm.

In these peak ranges, the carbons in the side-chain methyl groups in thesecond unit (propylene unit) of the head-to-tail bonded triad sequences(i) and (ii) give peaks as shown in Table 1.

TABLE 1 Peak range of methyl group carbons (19.5-21.9 ppm) Third rangeChemical First range Second range 19.5-20.2 shift 21.0-21.9 ppm20.2-21.0 ppm ppm Sequence PPP (mm) PPP (mr) PPP (rr) (i) Head-to-tailSequence PPB (mm) PPB (mr) bonding (ii) BPB (mm) BPB (mr) type PPB (rr)BPB (rr)

In the table, P denotes a constituent unit derived from propylene, and Bdenotes that derived from 1-butene. Of the triad sequences (i) and (ii)with head-to-tail bondings given in Table 1, the triad sequence (i)consisting of three propylene units PPP (mm), PPP (mr) and PPP (rr) areillustrated below in terms of zigzag structures as a result of branchedmethyl groups. These illustrations for mm, mr and rr bondings also applyto the triad sequence (ii) that contains butene unit(s) (PPB and BPB).

In the first range, the methyl groups in the second propylene unit ofthe mm-bonded triad sequences PPP, PPB and BPB give resonance peaks. Thesecond range shows resonance peaks of the methyl groups in the secondpropylene unit of the mr-bonded triad sequences PPP, PPB and BPB, andthose assigned to the methyl groups in the second propylene unit of therr-bonded triad sequences PPB and BPB.

In the third range, the methyl group in the second propylene unit of therr-cbonded triad sequence PPP gives a resonance peak. Therefore, thetriad tacticity (mm fraction) of the propylene/1-butene random copolymer(PBR) is a proportion (percentage) of the area of the peaks appearing inthe range of 21.0 to 21.9 ppm (first range) relative to the total (100%)of the areas of the peaks found within 19.5 to 21.9 ppm (methyl groupcarbon range) according to measurement by ¹³C-NMR spectroscopy(hexachlorobutadiene solution, with tetramethylsilane as the reference)based on the side-chain methyl groups in the second propylene unit of(i) the triad sequence of head-to-tail bonded propylene units or in thesecond propylene unit of (ii) the triad sequence of propylene and buteneunits that are head-to-tail bonded with a propylene unit as the secondunit. Specifically, the mm fraction may be derived from the followingformula (1):

$\begin{matrix}{{m\; m\mspace{14mu}{fraction}\mspace{14mu}(\%)} = {\frac{\begin{matrix}{{Intensities}\mspace{14mu}{of}\mspace{14mu}{methyl}\mspace{14mu}{groups}} \\\left\lbrack {{{PPP}\left( {m\; m} \right)} + {{PPB}\left( {m\; m} \right)} + {{BPB}\left( {m\; m} \right)}} \right\rbrack\end{matrix}}{\begin{matrix}{{Intensities}\mspace{14mu}{of}\mspace{14mu}{methyl}\mspace{14mu}{groups}} \\\begin{bmatrix}{{{PPP}\left( {m\; m} \right)} + {{PPB}\left( {m\; m} \right)} +} \\{{{BPB}\left( {m\; m} \right)} + {{PPP}({mr})} +} \\{{{PPB}({mr})} + {{BPB}({mr})} +} \\{{{PPP}({rr})} + {{PPB}({rr})} + {{BPB}({rr})}}\end{bmatrix}\end{matrix}} \times 100}} & (1)\end{matrix}$

The mm fraction of the propylene/1-butene random copolymer (PBR)obtained as described above ranges from 85 to 97.5%, preferably from 87to 97%, and more preferably from 90 to 97%. Importantly, the mm fractionin the present invention should fall in a moderate range. The mmfraction within the above range enables the copolymer to have a lowermelting point while containing a relatively large amount of propylene.The propylene/1-butene random copolymer (PBR) contains, in addition tothe head-to-tail bonded triad sequences (i) and (ii), a minor amount ofstructural units that include irregularly arranged units as illustratedin the formulae (iii), (iv) and (v). The side-chain methyl groups inthese other propylene units also show peaks within the above methylgroup carbon range (19.5 to 21.9 ppm).

In the methyl groups in these structural units as illustrated informulae (iii), (iv) and (v), the methyl group carbons A and B giveresonance peaks at 17.3 ppm and 17.0 ppm respectively, outside the firstto third peak ranges (19.5 to 21.9 ppm). Since the carbons A and B arenot involved in forming the triad propylene sequence with head-to-tailbondings, the triad tacticity (mm fraction) should be calculatedexcluding them.

Meanwhile, the peaks assigned to the methyl group carbons C, D and D′appear in the second range, and those assigned to the methyl groupcarbons E and E′ appear in the third range.

Therefore, the first to third peak ranges for the methyl group carbonsshow the peaks assigned to the PPE-methyl group (the side-chain methylgroup in a propylene-propylene-ethylene sequence) (near 20.7 ppm), theEPE-methyl group (the side-chain methyl group in anethylene-propylene-ethylene sequence) (near 19.8 ppm), the methyl groupC, the methyl group D, the methyl group D′, the methyl group E and themethyl group E′.

As described above, the peak ranges of methyl group carbons show peaksassigned to the methyl groups in sequences other than the head-to-tailbonded triad sequences (i) and (ii). Therefore, these peaks arecalibrated as described below for determination of the mm fraction bythe above formula.

The peak area of the PPE-methyl group can be obtained from the peak areaof the PPE-methine group (resonance near 30.6 ppm). The peak area of theEPE-methyl group can be obtained from the peak area of the EPE-methinegroup (resonance near 32.9 ppm).

The peak area of the methyl group C can be obtained from the peak areaof the adjacent methine group (resonance near 31.3 ppm). The peak areaof the methyl group D is half the combined peak areas of α,β methylenecarbons in the structural unit (iv) (resonance near 34.3 ppm and near34.5 ppm). The peak area of the methyl group D′ can be obtained from thepeak area of the methine group (resonance near 33.3 ppm) adjacent to themethyl group E′ in the structural unit (v).

The peak area of the methyl group E can be obtained from the peak areaof the adjacent methine carbon (resonance near 33.7 ppm). The peak areaof the methyl group E′ can be obtained from the peak area of theadjacent methine carbon (resonance near 33.3 ppm).

Accordingly, subtracting these peak areas from the total peak areas inthe second and third ranges gives an area of the peaks assigned to themethyl groups in the head-to-tail bonded triad propylene sequences (i)and (ii).

The peak area of the methyl groups in the head-to-tail bonded triadpropylene sequences (i) and (ii) provided by the above subtraction isput in the above formula to work out the mm fraction.

The carbon peaks found in the spectrum may be assigned by reference tothe literature “Polymer, 30, 1350 (1989)”.

(3) Intrinsic Viscosity [η]

The propylene/1-butene random copolymer (PBR) has an intrinsic viscosity[η] of 0.1 to 12 dl/g, preferably 0.5 to 10 dl/g, and more preferably 1to 5 dl/g as measured in decalin at 135° C.

(4) Molecular Weight Distribution

The propylene/1-butene random copolymer (PBR) has a molecular weightdistribution (Mw/Mn) of 3 or less, preferably from 1.8 to 3.0, and morepreferably from 1.9 to 2.5 according to measurement by gel permeationchromatography (GPC).

(5) Randomness

The propylene/1-butene random copolymer (PBR) has a parameter value B,indicative of randomness of distributed monomer sequences, of 0.9 to1.3, preferably 0.95 to 1.25, and more preferably 0.95 to 1.2.

The parameter value B has been proposed by B. D. Cole-man and T. G. Fox(J. Polym. Sci., A1, 3183 (1963)), and can be defined as follows:B=P ₁₂/(2P ₁ ·P ₂)wherein P₁ and P₂ are fractions of first and second monomersrespectively, and P₁₂ is a proportion of (first monomer)-(secondmonomer) sequences relative to all the dyad monomer sequences.

When the B-value is 1, the Bernoulli's statistics applies. When theB-value is smaller than 1 (B<1), the copolymer is arranged in the formof block chains. On the other hand, when the B-value is greater than 1(B>1), the copolymer is arranged in the form of alternate chains. Whenthe B-value is 2 (B=2), the copolymer is an alternating copolymer.

(6)

The propylene/1-butene random copolymer (PBR) has a melting point (Tm)of 40 to 120° C., preferably 50 to 100° C., and more preferably 55 to90° C. as measured on a differential scanning calorimeter. The meltingpoint (Tm) and the content (M) of 1-butene constituent units (mol %)satisfy the relation of:146 exp(−0.022M)≧Tm≧125 exp(−0.032M),preferably146 exp(−0.024M)≧Tm≧125 exp(−0.032M),and more preferably146 exp(−0.0265M)≧Tm≧125 exp(−0.032M).

When the melting point and the butene content have the abovecorrelation, the copolymer can display a lowered melting point whilecontaining a relatively large amount of propylene. As a result, thecopolymer can display higher crystallization rate in spite of a lowmelting point.

The propylene/1-butene random copolymer (PBR) according to the presentinvention may contain a minor amount of irregularly bonded (irregularlyarranged) propylene units based on 2,1-insertion or 1,3-insertion in thepropylene sequence.

When polymerized, the propylene generally forms a head-to-tail bondedsequence with 1,2-insertion (in which the methylene groups bond acatalyst), but 2,1-insertion or 1,3-insertion also unusually occurs. Thepropylene units having 2,1-insertion or 1,3-insertion form irregularlyarranged units as represented by the formulae (iii), (iv) and (v). Aswith the stereoregularity, the proportion of the propylene units with2,1-insertion and 1,3-insertion relative to the polymer structural unitsmay be determined from the following formula based on data obtained froma ¹³C-NMR spectrum with reference to the literature “Polymer, 30, 1350(1989).”

The proportion of the irregularly arranged propylene units based on2,1-insertion can be obtained from the formula:

$\begin{matrix}{{Proportion}\mspace{14mu}{of}} \\{{irregularly}\mspace{14mu}{arranged}} \\{{units}\mspace{14mu}{with}} \\{2,1\text{-}{insertion}}\end{matrix} = {\frac{\begin{Bmatrix}{{0.5\; I\;{{\alpha\beta}\left( {{structures}\mspace{14mu}({iii})\mspace{14mu}{and}\mspace{14mu}(v)} \right)}} +} \\{0.25\; I\;{{\alpha\beta}\left( {{structure}\mspace{14mu}({iv})} \right)}}\end{Bmatrix}}{\begin{matrix}{{I\;{\alpha\alpha}} + {I\;{{\alpha\beta}\left( {{structures}\mspace{14mu}({iii})\mspace{14mu}{and}\mspace{14mu}(v)} \right)}} +} \\\left. {0.5\left( {{I\;{\alpha\gamma}} + {I\;{{\alpha\beta}\left( {{structure}\mspace{14mu}({iv})} \right)}} + {I\;{\alpha\delta}}} \right)} \right\}\end{matrix}} \times 100}$

When determination of the peak areas of Iαβ, etc. is difficult owing tothe overlapping peaks, calibration can be made with the peaks of carbonthat have corresponding areas.

The propylene/1-butene random copolymer (PBR) according to the presentinvention may contain the irregularly bonded propylene units in terms of2,1-insertion in an amount of 0.01% or above, specifically about 0.01 to1.0% relative to all the propylene structural units.

The proportion of the irregularly arranged propylene units based on1,3-insertion in the propylene/1-butene random copolymer (PBR) can beobtained from the peak of βγ peak (resonance near 27.4 ppm).

The propylene/1-butenerandom copolymer according to the presentinvention may contain the irregularly bonded propylene units based on1,3-insertion in an amount of 0.05% or less.

An exemplary process for the production of the propylene/1-butene randomcopolymer (PBR) according to the present invention will be given below.

The propylene/1-butene random copolymer (PBR) may be prepared bycopolymerizing propylene and 1-butene in the presence of an olefinpolymerization catalyst that comprises:

a transition metal compound (1a),

and at least one compound selected from:

an organoaluminum oxy-compound, and/or

a compound capable of forming an ion pair by reacting with thetransition metal compound (1a), and

an organoaluminum compound.

The above transition metal compound (1a) has the formula (1a):

wherein R³ is a hydrocarbon group or a silicon-containing group; R¹, R²and R⁴, which may be the same or different, are each a hydrogen atom, ahydrocarbon group or a silicon-containing group; R⁵, R⁶, R⁷, R⁸, R⁹,R¹⁰, R¹¹, R¹², R¹³ and R¹⁴, which may be the same or different, are eacha hydrogen atom, a hydrocarbon group or a silicon-containing group;neighboring substituent groups of R⁵ to R¹² may link together to form aring; R¹³ and R¹⁴, which may be the same or different, may link togetherto form a ring; M denotes a Group-4 transition metal; Y denotes a carbonatom; Q denotes a halogen atom, a hydrocarbon group, an anionic ligandor a neutral ligand capable of coordination by a lone pair of electrons,and may be the same or different when plural; and j is an integer of 1to 4.

Preferably, R¹ in the transition metal compound (1a) of the formula (1a)is a hydrocarbon group or a silicon-containing group.

Exemplary compounds having the formula (1a) include bridged metallocenecompounds with C1 symmetry, such asisopropylidene(3-tert-butylcyclopentadienyl)(fluorenyl)zirconiumdichloride,isopropylidene(3-tert-butylcyclopentadienyl)(2,7-di-tert-butylfluorenyl)zirconiumdichloride,isopropylidene(3-tert-butylcyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirconiumdichloride,isopropylidene(3-tert-butylcyclopentadienyl)(octamethyloctahydridodibenzofluorenyl)zirconiumdichloride,diphenylmethylene(3-tert-butylcyclopentadienyl)(fluorenyl)zirconiumdichloride,diphenylmethylene(3-tert-butylcyclopentadienyl)(2,7-di-tert-butylfluorenyl)zirconiumdichloride,diphenylmethylene(3-tert-butylcyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirconiumdichloride,diphenylmethylene(3-tert-butylcyclopentadienyl)(octamethyloctahydridodibenzofluorenyl)zirconiumdichloride,cyclohexylidene(3-tert-butylcyclopentadienyl)(fluorenyl)zirconiumdichloride,cyclohexylidene(3-tert-butylcyclopentadienyl)(2,7-di-tert-butylfluorenyl)zirconiumdichloride,cyclohexylidene(3-tert-butylcyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirconiumdichloride,cyclohexylidene(3-tert-butylcyclopentadienyl)(octamethyloctahydridodibenzofluorenyl)zirconiumdichloride,phenylmethylmethylene(3-tert-butylcyclopentadienyl)(fluorenyl)zirconiumdichloride,phenylmethylmethylene(3-tert-butylcyclopentadienyl)(2,7-di-tert-butylfluorenyl)zirconiumdichloride,phenylmethylmethylene(3-tert-butylcyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirconiumdichloride,phenylmethylmethylene(3-tert-butylcyclopentadienyl)(octamethyloctahydridodibenzofluorenyl)zirconiumdichloride,isopropylidene(3-trimethylsilylcyclopentadienyl)(fluorenyl)zirconiumdichloride,isopropylidene(3-trimethylsilylcyclopentadienyl)(2,7-di-tert-butylfluorenyl)zirconiumdichloride,isopropylidene(3-trimethylsilylcyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirconiumdichloride,isopropylidene(3-trimethylsilylcyclopentadienyl)(octamethyloctahydridodibenzofluorenyl)zirconiumdichloride,diphenylmethylene(3-trimethylsilylcyclopentadienyl)(fluorenyl)zirconiumdichloride,diphenylmethylene(3-trimethylsilylcyclopentadienyl)(2,7-di-tert-butylfluorenyl)zirconiumdichloride,diphenylmethylene(3-trimethylsilylcyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirconiumdichloride,diphenylmethylene(3-trimethylsilylcyclopentadienyl)(octamethyloctahydridodibenzofluorenyl)zirconiumdichloride,cyclohexylidene(3-trimethylsilylcyclopentadienyl)(fluorenyl)zirconiumdichloride,cyclohexylidene(3-trimethylsilylcyclopentadienyl)(2,7-di-tert-butylfluorenyl)zirconiumdichloride,cyclohexylidene(3-trimethylsilylcyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirconiumdichloride,cyclohexylidene(3-trimethylsilylcyclopentadienyl)(octamethyloctahydridodibenzofluorenyl)zirconiumdichloride,phenylmethylmethylene(3-trimethylsilylcyclopentadienyl)(fluorenyl)zirconiumdichloride,phenylmethylmethylene(3-trimethylsilylcyclopentadienyl)(2,7-di-tert-butylfluorenyl)zirconiumdichloride,phenylmethylmethylene(3-trimethylsilylcyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirconiumdichloride,phenylmethylmethylene(3-trimethylsilylcyclopentadienyl)(octamethyloctahydridodibenzofluorenyl)zirconiumdichloride, isopropylidene(3-phenylcyclopentadienyl)(fluorenyl)zirconiumdichloride,isopropylidene(3-phenylcyclopentadienyl)(2,7-di-tert-butylfluorenyl)zirconiumdichloride,isopropylidene(3-phenylcyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirconiumdichloride,isopropylidene(3-phenylcyclopentadienyl)(octamethyloctahydridodibenzofluorenyl)zirconiumdichloride,diphenylmethylene(3-phenylcyclopentadienyl)(fluorenyl)zirconiumdichloride,diphenylmethylene(3-phenylcyclopentadienyl)(2,7-di-tert-butylfluorenyl)zirconiumdichloride,diphenylmethylene(3-phenylcyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirconiumdichloride,diphenylmethylene(3-phenylcyclopentadienyl)(octamethyloctahydridodibenzofluorenyl)zirconiumdichloride,cyclohexylidene(3-phenylcyclopentadienyl)(fluorenyl)zirconiumdichloride,cyclohexylidene(3-phenylcyclopentadienyl)(2,7-di-tert-butylfluorenyl)zirconiumdichloride,cyclohexylidene(3-phenylcyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirconiumdichloride,cyclohexylidene(3-phenylcyclopentadienyl)(octamethyloctahydridodibenzofluorenyl)zirconiumdichloride,phenylmethylmethylene(3-phenylcyclopentadienyl)(fluorenyl)zirconiumdichloride,phenylmethylmethylene(3-phenylcyclopentadienyl)(2,7-di-tert-butylfluorenyl)zirconiumdichloride,phenylmethylmethylene(3-phenylcyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirconiumdichloride,phenylmethylmethylene(3-phenylcyclopentadienyl)(octamethyloctahydridodibenzofluorenyl)zirconiumdichloride,isopropylidene(3-adamantylcyclopentadienyl)(fluorenyl)zirconiumdichloride,isopropylidene(3-adamantylcyclopentadienyl)(2,7-di-tert-butylfluorenyl)zirconiumdichloride,isopropylidene(3-adamantylcyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirconiumdichloride,isopropylidene(3-adamantylcyclopentadienyl)(octamethyloctahydridodibenzofluorenyl)zirconiumdichloride,diphenylmethylene(3-adamantylcyclopentadienyl)(fluorenyl)zirconiumdichloride,diphenylmethylene(3-adamantylcyclopentadienyl)(2,7-di-tert-butylfluorenyl)zirconiumdichloride,diphenylmethylene(3-adamantylcyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirconiumdichloride,diphenylmethylene(3-adamantylcyclopentadienyl)(octamethyloctahydridodibenzofluorenyl)zirconiumdichloride,cyclohexylidene(3-adamantylcyclopentadienyl)(fluorenyl)zirconiumdichloride,cyclohexylidene(3-adamantylcyclopentadienyl)(2,7-di-tert-butylfluorenyl)zirconiumdichloride,cyclohexylidene(3-adamantylcyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirconiumdichloride,cyclohexylidene(3-adamantylcyclopentadienyl)(octamethyloctahydridodibenzofluorenyl)zirconiumdichloride,phenylmethylmethylene(3-adamantylcyclopentadienyl)(fluorenyl)zirconiumdichloride,phenylmethylmethylene(3-adamantylcyclopentadienyl)(2,7-di-tert-butylfluorenyl)zirconiumdichloride,phenylmethylmethylene(3-adamantylcyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirconiumdichloride,phenylmethylmethylene(3-adamantylcyclopentadienyl)(octamethyloctahydridodibenzofluorenyl)zirconiumdichloride,isopropylidene(3-adamantyl-3′-methylcyclopentadienyl)(fluorenyl)zirconiumdichloride,isopropylidene(3-adamantyl-3′-methylcyclopentadienyl)(2,7-di-tert-butylfluorenyl)zirconiumdichloride,isopropylidene(3-adamantyl-3′-methylcyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirconiumdichloride,isopropylidene(3-adamantyl-3′-methylcyclopentadienyl)(octamethyloctahydridodibenzofluorenyl)zirconiumdichloride,diphenylmethylene(3-adamantyl-3′-methylcyclopentadienyl)(fluorenyl)zirconiumdichloride,diphenylmethylene(3-adamantyl-3′-methylcyclopentadienyl)(2,7-di-tert-butylfluorenyl)zirconiumdichloride,diphenylmethylene(3-adamantyl-3′-methylcyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirconiumdichloride,diphenylmethylene(3-adamantyl-3′-methylcyclopentadienyl)(octamethyloctahydridodibenzofluorenyl)zirconiumdichloride,cyclohexylidene(3-adamantyl-3′-methylcyclopentadienyl)(fluorenyl)zirconiumdichloride,cyclohexylidene(3-adamantyl-3′-methylcyclopentadienyl)(2,7-di-tert-butylfluorenyl)zirconiumdichloride,cyclohexylidene(3-adamantyl-3′-methylcyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirconiumdichloride,cyclohexylidene(3-adamantyl-3′-methylcyclopentadienyl)(octamethyloctahydridodibenzofluorenyl)zirconiumdichloride,phenylmethylmethylene(3-adamantyl-3′-methylcyclopentadienyl)(fluorenyl)zirconiumdichloride,phenylmethylmethylene(3-adamantyl-3′-methylcyclopentadienyl)(2,7-di-tert-butylfluorenyl)zirconiumdichloride,phenylmethylmethylene(3-adamantyl-3′-methylcyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirconiumdichloride,phenylmethylmethylene(3-adamantyl-3′-methylcyclopentadienyl)(octamethyloctahydridodibenzofluorenyl)zirconiumdichloride, isopropylidene(3-furylcyclopentadienyl)(fluorenyl)zirconiumdichloride,isopropylidene(3-furylcyclopentadienyl)(2,7-di-tert-butylfluorenyl)zirconiumdichloride,isopropylidene(3-furylcyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirconiumdichloride,isopropylidene(3-furylcyclopentadienyl)(octamethyloctahydridodibenzofluorenyl)zirconiumdichloride,diphenylmethylene(3-furylcyclopentadienyl)(fluorenyl)zirconiumdichloride,diphenylmethylene(3-furylcyclopentadienyl)(2,7-di-tert-butylfluorenyl)zirconiumdichloride,diphenylmethylene(3-furylcyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirconiumdichloride,diphenylmethylene(3-furylcyclopentadienyl)(octamethyloctahydridodibenzofluorenyl)zirconiumdichloride, cyclohexylidene(3-furylcyclopentadienyl)(fluorenyl)zirconiumdichloride,cyclohexylidene(3-furylcyclopentadienyl)(2,7-di-tert-butylfluorenyl)zirconiumdichloride,cyclohexylidene(3-furylcyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirconiumdichloride,cyclohexylidene(3-furylcyclopentadienyl)(octamethyloctahydridodibenzofluorenyl)zirconiumdichloride,phenylmethylmethylene(3-furylcyclopentadienyl)(fluorenyl)zirconiumdichloride,phenylmethylmethylene(3-furylcyclopentadienyl)(2,7-di-tert-butylfluorenyl)zirconiumdichloride,phenylmethylmethylene(3-furylcyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirconiumdichloride,phenylmethylmethylene(3-furylcyclopentadienyl)(octamethyloctahydridodibenzofluorenyl)zirconiumdichloride,isopropylidene(3-thienylcyclopentadienyl)(fluorenyl)zirconiumdichloride,isopropylidene(3-thienylcyclopentadienyl)(2,7-di-tert-butylfluorenyl)zirconiumdichloride,isopropylidene(3-thienylcyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirconiumdichloride,isopropylidene(3-thienylcyclopentadienyl)(octamethyloctahydridodibenzofluorenyl)zirconiumdichloride,diphenylmethylene(3-thienylcyclopentadienyl)(fluorenyl)zirconiumdichloride,diphenylmethylene(3-thienylcyclopentadienyl)(2,7-di-tert-butylfluorenyl)zirconiumdichloride,diphenylmethylene(3-thienylcyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirconiumdichloride,diphenylmethylene(3-thienylcyclopentadienyl)(octamethyloctahydridodibenzofluorenyl)zirconiumdichloride,cyclohexylidene(3-thienylcyclopentadienyl)(fluorenyl)zirconiumdichloride,cyclohexylidene(3-thienylcyclopentadienyl)(2,7-di-tert-butylfluorenyl)zirconiumdichloride,cyclohexylidene(3-thienylcyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirconiumdichloride,cyclohexylidene(3-thienylcyclopentadienyl)(octamethyloctahydridodibenzofluorenyl)zirconiumdichloride,phenylmethylmethylene(3-thienylcyclopentadienyl)(fluorenyl)zirconiumdichloride,phenylmethylmethylene(3-thienylcyclopentadienyl)(2,7-di-tert-butylfluorenyl)zirconiumdichloride,phenylmethylmethylene(3-thienylcyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirconiumdichloride,phenylmethylmethylene(3-thienylcyclopentadienyl)(octamethyloctahydridodibenzofluorenyl)zirconiumdichloride,isopropylidene(3-tert-butyl-5-methylcyclopentadienyl)(fluorenyl)zirconiumdichloride,isopropylidene(3-tert-butyl-5-methylcyclopentadienyl)(2,7-di-tert-butylfluorenyl)zirconiumdichloride,isopropylidene(3-tert-butyl-5-methylcyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirconiumdichloride, isopropylidene(3-tert-butyl-5-methylcyclopentadienyl)(octamethyloctahydridodibenzofluorenyl)zirconium dichloride,diphenylmethylene(3-tert-butyl-5-methylcyclopentadienyl)(fluorenyl)zirconium dichloride,diphenylmethylene(3-tert-butyl-5-methylcyclopentadienyl)(2,7-di-tert-butylfluorenyl)zirconiumdichloride,diphenylmethylene(3-tert-butyl-5-methylcyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirconiumdichloride,diphenylmethylene(3-tert-butyl-5-methylcyclopentadienyl)(octamethyloctahydridodibenzofluorenyl)zirconiumdichloride,cyclohexylidene(3-tert-butyl-5-methylcyclopentadienyl)(fluorenyl)zirconiumdichloride,cyclohexylidene(3-tert-butyl-5-methylcyclopentadienyl)(2,7-di-tert-butylfluorenyl)zirconiumdichloride,cyclohexylidene(3-tert-butyl-5-methylcyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirconiumdichloride,cyclohexylidene(3-tert-butyl-5-methylcyclopentadienyl)(octamethyloctahydridodibenzofluorenyl)zirconiumdichloride,phenylmethylmethylene(3-tert-butyl-5-methylcyclopentadienyl)(fluorenyl)zirconiumdichloride,phenylmethylmethylene(3-tert-butyl-5-methylcyclopentadienyl)(2,7-di-tert-butylfluorenyl)zirconiumdichloride,phenylmethylmethylene(3-tert-butyl-5-methylcyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirconiumdichloride,phenylmethylmethylene(3-tert-butyl-5-methylcyclopentadienyl)(octamethyloctahydridodibenzofluorenyl)zirconiumdichloride,isopropylidene(3-trimethylsilyl-5-methylcyclopentadienyl)(fluorenyl)zirconiumdichloride,isopropylidene(3-trimethylsilyl-5-methylcyclopentadienyl)(2,7-di-tert-butylfluorenyl)zirconiumdichloride,isopropylidene(3-trimethylsilyl-5-methylcyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirconiumdichloride,isopropylidene(3-trimethylsilyl-5-methylcyclopentadienyl)(octamethyloctahydridodibenzofluorenyl)zirconiumdichloride,diphenylmethylene(3-trimethylsilyl-5-methylcyclopentadienyl)(fluorenyl)zirconiumdichloride,diphenylmethylene(3-trimethylsilyl-5-methylcyclopentadienyl)(2,7-di-tert-butylfluorenyl)zirconiumdichloride,diphenylmethylene(3-trimethylsilyl-5-methylcyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirconiumdichloride,diphenylmethylene(3-trimethylsilyl-5-methylcyclopentadienyl)(octamethyloctahydridodibenzofluorenyl)zirconiumdichloride,cyclohexylidene(3-trimethylsilyl-5-methylcyclopentadienyl)(fluorenyl)zirconiumdichloride,cyclohexylidene(3-trimethylsilyl-5-methylcyclopentadienyl)(2,7-di-tert-butylfluorenyl)zirconiumdichloride,cyclohexylidene(3-trimethylsilyl-5-methylcyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirconiumdichloride,cyclohexylidene(3-trimethylsilyl-5-methylcyclopentadienyl)(octamethyloctahydridodibenzofluorenyl)zirconiumdichloride,phenylmethylmethylene(3-trimethylsilyl-5-methylcyclopentadienyl)(fluorenyl)zirconiumdichloride,phenylmethylmethylene(3-trimethylsilyl-5-methylcyclopentadienyl)(2,7-di-tert-butylfluorenyl)zirconiumdichloride,phenylmethylmethylene(3-trimethylsilyl-5-methylcyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirconiumdichloride,phenylmethylmethylene(3-trimethylsilyl-5-methylcyclopentadienyl)(octamethyloctahydridodibenzofluorenyl)zirconiumdichloride,isopropylidene(3-phenyl-5-methylcyclopentadienyl)(fluorenyl)zirconiumdichloride,isopropylidene(3-phenyl-5-methylcyclopentadienyl)(2,7-di-tert-butylfluorenyl)zirconiumdichloride,isopropylidene(3-phenyl-5-methylcyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirconiumdichloride,isopropylidene(3-phenyl-5-methylcyclopentadienyl)(octamethyloctahydridodibenzofluorenyl)zirconiumdichloride,diphenylmethylene(3-phenyl-5-methylcyclopentadienyl)(fluorenyl)zirconiumdichloride,diphenylmethylene(3-phenyl-5-methylcyclopentadienyl)(2,7-di-tert-butylfluorenyl)zirconiumdichloride,diphenylmethylene(3-phenyl-5-methylcyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirconiumdichloride,diphenylmethylene(3-phenyl-5-methylcyclopentadienyl)(octamethyloctahydridodibenzofluorenyl)zirconiumdichloride,cyclohexylidene(3-phenyl-5-methylcyclopentadienyl)(fluorenyl)zirconiumdichloride,cyclohexylidene(3-phenyl-5-methylcyclopentadienyl)(2,7-di-tert-butylfluorenyl)zirconiumdichloride,cyclohexylidene(3-phenyl-5-methylcyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirconiumdichloride,cyclohexylidene(3-phenyl-5-methylcyclopentadienyl)(octamethyloctahydridodibenzofluorenyl)zirconiumdichloride,phenylmethylmethylene(3-phenyl-5-methylcyclopentadienyl)(fluorenyl)zirconiumdichloride,phenylmethylmethylene(3-phenyl-5-methylcyclopentadienyl)(2,7-di-tert-butylfluorenyl)zirconiumdichloride,phenylmethylmethylene(3-phenyl-5-methylcyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirconiumdichloride,phenylmethylmethylene(3-phenyl-5-methylcyclopentadienyl)(octamethyloctahydridodibenzofluorenyl)zirconiumdichloride,isopropylidene(3-adamantyl-5-methylcyclopentadienyl)(fluorenyl)zirconiumdichloride,isopropylidene(3-adamantyl-5-methylcyclopentadienyl)(2,7-di-tert-butylfluorenyl)zirconiumdichloride,isopropylidene(3-adamantyl-5-methylcyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirconiumdichloride,isopropylidene(3-adamantyl-5-methylcyclopentadienyl)(octamethyloctahydridodibenzofluorenyl)zirconiumdichloride,diphenylmethylene(3-adamantyl-5-methylcyclopentadienyl)(fluorenyl)zirconiumdichloride,diphenylmethylene(3-adamantyl-5-methylcyclopentadienyl)(2,7-di-tert-butylfluorenyl)zirconiumdichloride,diphenylmethylene(3-adamantyl-5-methylcyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirconiumdichloride,diphenylmethylene(3-adamantyl-5-methylcyclopentadienyl)(octamethyloctahydridodibenzofluorenyl)zirconiumdichloride,cyclohexylidene(3-adamantyl-5-methylcyclopentadienyl)(fluorenyl)zirconiumdichloride,cyclohexylidene(3-adamantyl-5-methylcyclopentadienyl)(2,7-di-tert-butylfluorenyl)zirconiumdichloride,cyclohexylidene(3-adamantyl-5-methylcyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirconiumdichloride,cyclohexylidene(3-adamantyl-5-methylcyclopentadienyl)(octamethyloctahydridodibenzofluorenyl)zirconiumdichloride,phenylmethylmethylene(3-adamantyl-5-methylcyclopentadienyl)(fluorenyl)zirconiumdichloride,phenylmethylmethylene(3-adamantyl-5-methylcyclopentadienyl)(2,7-di-tert-butylfluorenyl)zirconiumdichloride,phenylmethylmethylene(3-adamantyl-5-methylcyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirconiumdichloride,phenylmethylmethylene(3-adamantyl-5-methylcyclopentadienyl)(octamethyloctahydridodibenzofluorenyl)zirconiumdichloride,isopropylidene(3-adamantyl-3′-methyl-5-methylcyclopentadienyl)(fluorenyl)zirconiumdichloride,isopropylidene(3-adamantyl-3′-methyl-5-methylcyclopentadienyl)(2,7-di-tert-butylfluorenyl)zirconiumdichloride,isopropylidene(3-adamantyl-3′-methyl-5-methylcyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirconiumdichloride,isopropylidene(3-adamantyl-3′-methyl-5-methylcyclopentadienyl)(octamethyloctahydridodibenzofluorenyl)zirconiumdichloride,diphenylmethylene(3-adamantyl-3′-methyl-5-methylcyclopentadienyl)(fluorenyl)zirconiumdichloride,diphenylmethylene(3-adamantyl-3′-methyl-5-methylcyclopentadienyl)(2,7-di-tert-butylfluorenyl)zirconiumdichloride,diphenylmethylene(3-adamantyl-3′-methyl-5-methylcyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirconiumdichloride,diphenylmethylene(3-adamantyl-3′-methyl-5-methylcyclopentadienyl)(octamethyloctahydridodibenzofluorenyl)zirconiumdichloride,cyclohexylidene(3-adamantyl-3′-methyl-5-methylcyclopentadienyl)(fluorenyl)zirconiumdichloride,cyclohexylidene(3-adamantyl-3′-methyl-5-methylcyclopentadienyl)(2,7-di-tert-butylfluorenyl)zirconiumdichloride,cyclohexylidene(3-adamantyl-3′-methyl-5-methylcyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirconiumdichloride,cyclohexylidene(3-adamantyl-3′-methyl-5-methylcyclopentadienyl)(octamethyloctahydridodibenzofluorenyl)zirconiumdichloride,phenylmethylmethylene(3-adamantyl-3′-methyl-5-methylcyclopentadienyl)(fluorenyl)zirconiumdichloride,phenylmethylmethylene(3-adamantyl-3′-methyl-5-methylcyclopentadienyl)(2,7-di-tert-butylfluorenyl)zirconiumdichloride,phenylmethylmethylene(3-adamantyl-3′-methyl-5-methylcyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirconiumdichloride,phenylmethylmethylene(3-adamantyl-3′-methyl-5-methylcyclopentadienyl)(octamethyloctahydridodibenzofluorenyl)zirconiumdichloride,isopropylidene(3-furyl-5-methylcyclopentadienyl)(fluorenyl)zirconiumdichloride,isopropylidene(3-furyl-5-methylcyclopentadienyl)(2,7-di-tert-butylfluorenyl)zirconiumdichloride,isopropylidene(3-furyl-5-methylcyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirconiumdichloride,isopropylidene(3-furyl-5-methylcyclopentadienyl)(octamethyloctahydridodibenzofluorenyl)zirconiumdichloride,diphenylmethylene(3-furyl-5-methylcyclopentadienyl)(fluorenyl)zirconiumdichloride,diphenylmethylene(3-furyl-5-methylcyclopentadienyl)(2,7-di-tert-butylfluorenyl)zirconiumdichloride,diphenylmethylene(3-furyl-5-methylcyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirconiumdichloride,diphenylmethylene(3-furyl-5-methylcyclopentadienyl)(octamethyloctahydridodibenzofluorenyl)zirconiumdichloride,cyclohexylidene(3-furyl-5-methylcyclopentadienyl)(fluorenyl)zirconiumdichloride,cyclohexylidene(3-furyl-5-methylcyclopentadienyl)(2,7-di-tert-butylfluorenyl)zirconiumdichloride,cyclohexylidene(3-furyl-5-methylcyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirconiumdichloride,cyclohexylidene(3-furyl-5-methylcyclopentadienyl)(octamethyloctahydridodibenzofluorenyl)zirconiumdichloride,phenylmethylmethylene(3-furyl-5-methylcyclopentadienyl)(fluorenyl)zirconiumdichloride,phenylmethylmethylene(3-furyl-5-methylcyclopentadienyl)(2,7-di-tert-butylfluorenyl)zirconiumdichloride,phenylmethylmethylene(3-furyl-5-methylcyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirconiumdichloride,phenylmethylmethylene(3-furyl-5-methylcyclopentadienyl)(octamethyloctahydridodibenzofluorenyl)zirconiumdichloride,isopropylidene(3-thienyl-5-methylcyclopentadienyl)(fluorenyl)zirconiumdichloride,isopropylidene(3-thienyl-5-methylcyclopentadienyl)(2,7-di-tert-butylfluorenyl)zirconiumdichloride,isopropylidene(3-thienyl-5-methylcyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirconiumdichloride,isopropylidene(3-thienyl-5-methylcyclopentadienyl)(octamethyloctahydridodibenzofluorenyl)zirconiumdichloride,diphenylmethylene(3-thienyl-5-methylcyclopentadienyl)(fluorenyl)zirconiumdichloride,diphenylmethylene(3-thienyl-5-methylcyclopentadienyl)(2,7-di-tert-butylfluorenyl)zirconiumdichloride,diphenylmethylene(3-thienyl-5-methylcyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirconiumdichloride,diphenylmethylene(3-thienyl-5-methylcyclopentadienyl)(octamethyloctahydridodibenzofluorenyl)zirconiumdichloride,cyclohexylidene(3-thienyl-5-methylcyclopentadienyl)(fluorenyl)zirconiumdichloride,cyclohexylidene(3-thienyl-5-methylcyclopentadienyl)(2,7-di-tert-butylfluorenyl)zirconiumdichloride,cyclohexylidene(3-thienyl-5-methylcyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirconiumdichloride,cyclohexylidene(3-thienyl-5-methylcyclopentadienyl)(octamethyloctahydridodibenzofluorenyl)zirconiumdichloride,phenylmethylmethylene(3-thienyl-5-methylcyclopentadienyl)(fluorenyl)zirconiumdichloride,phenylmethylmethylene(3-thienyl-5-methylcyclopentadienyl)(2,7-di-tert-butylfluorenyl)zirconiumdichloride,phenylmethylmethylene(3-thienyl-5-methylcyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirconiumdichloride,phenylmethylmethylene(3-thienyl-5-methylcyclopentadienyl)(octamethyloctahydridodibenzofluorenyl)zirconiumdichloride, and dibromide compounds, dialkyl compounds and dialkoxycompounds of the above metallocene compounds, and correspondingmetallocene compounds to the above compounds except that the centralmetals are replaced with hafnium or titanium. The compounds listed aboveare just illustrative and do not limit the scope of the presentinvention.

The propylene elastomer (PBER) of the present invention contains:

(a) units derived from propylene in an amount of 50 to 85 mol %,preferably 60 to 85 mol %, and more preferably 65 to 80 mol %;

(b) units derived from 1-butene in an amount of 5 to 25 mol %,preferably 5 to 20 mol %, and more preferably 5 to 15 mol %; and

(c) units derived from ethylene in an amount of 10 to 25 mol %,preferably 13 to 25 mol %, and more preferably 13 to 23 mol %.

The propylene content and the ethylene content have a molar ratio(propylene/ethylene) of 89/11 to 70/30, preferably 89/11 to 75/25, andmore preferably 89/11 to 80/20. The propylene elastomer has a modulus intension (YM) of 40 MPa or less, preferably 30 MPa or less, and morepreferably 20 MPa or less as measured in accordance with JIS 6301.

The propylene elastomer (PBER) having the above properties exhibits hightransparency, excellent flexibility and good compatibility withpolypropylenes.

Preferably, the propylene elastomer (PBER) further has the followingproperties.

The propylene elastomer (PBER) has an mm fraction of 85 to 97.5%,preferably 87 to 97%, and more preferably 90 to 97% as determined by theprocedure for the propylene/1-butene random copolymer (PBR).Importantly, the mm fraction should fall within a moderate upper limit.The mm fraction within the above specific range enables the elastomer tohave a lower melting point while containing a relatively large amount ofpropylene.

The propylene elastomer (PBER) of the present invention has a molecularweight distribution (Mw/Mn) of 1 to 3, preferably 1.5 to 2.5 as measuredby gel permeation chromatography (GPC). The intrinsic viscosity of thepropylene elastomer (PBER) as measured in decalin at 135° C. ranges from0.1 to 5 dl/g, preferably from 1 to 3 dl/g. The propylene elastomer(PEER) of the present invention has a glass transition temperature (Tg)of −15 to −40° C., preferably −20 to −35° C., and has no melting point(Tm).

The propylene elastomer (PBER) of the present invention is preferablyproduced using the metallocene catalyst systems used for thepropylene/1-butene random copolymer (PBR). Specifically, the transitionmetal compound (1a) is preferable, and more preferably, R¹ of thetransition metal compound (1a) is a hydrocarbon group or asilicon-containing group.

The polypropylene composition (CC-1) according to the present inventioncontains the aforesaid polypropylene (PP-A) in an amount of 5 to 95 wt%, preferably 20 to 95 wt %, and more preferably 40 to 90 wt %, and thepropylene/1-butene random copolymer (PBR) in an amount of 95 to 5 wt %,preferably 80 to 5 wt %, and more preferably 60 to 10 wt %.

The polypropylene composition (CC-2) of the present invention containsthe crystalline polypropylene (PP-A) in an amount of 0 to 95 wt %,preferably 5 to 95 wt %, and more preferably 20 to 95 wt %, and thepropylene/1-butene random copolymer (PBR) in an amount of 5 to 100 wt %,preferably 5 to 95 wt %, and more preferably 5 to 80 wt %.

The polypropylene compositions (CC-1) and (CC-2) may be prepared byknown processes for the production of resin compositions. For example,the polypropylene (PP-A) and the propylene/1-butene random copolymer(PBR) may be melt kneaded.

The polypropylene compositions (CC-1) and (CC-2) of the presentinvention may contain additives or other resins in addition to thepolypropylene and the propylene/1-butene copolymer without adverselyaffecting the objects of the invention.

The additives include nucleating agents, antioxidants, hydrochloric acidabsorbers, heat stabilizers, light stabilizers, ultraviolet lightabsorbers, lubricants, anti-blocking agents, antistatic agents,flame-retardants, pigments, dyes, dispersants, copper inhibitors,neutralizing agents, foaming agents, plasticizers, anti-foaming agents,crosslinking agents, flow modifiers such as peroxides, and weld strengthimprovers.

Additives, including those listed above, that are conventionally usedfor the polyolefin resins may be employed without limitation.

The antioxidants include phenol-based, sulfur-based andphosphorous-based antioxidants. The phenol-based antioxidants includephenols, such as 2,6-di-tert-butyl-p-cresol, stearyl(3,3-dimethyl-4-hydroxybenzyl)thioglycolate,stearyl-β-(4-hydroxy-3,5-di-tert-butylphenol)propionate,distearyl-3,5-di-tert-butyl-4-hydroxybenzyl phosphonate,2,4,6-tris(3′,5′-di-tert-butyl-4′-hydroxybenzylthio)-1,3,5-triazine,distearyl (4-hydroxy-3-methyl-5-tert-butylbenzyl)malonate,2,2′-methylenebis(4-methyl-6-tert-butylphenol),4,4′-methylenebis(2,6-di-tert-butylphenol),2,2′-methylenebis[6-(1-methylcyclohexyl)p-cresol],bis[3,5-bis[4-hydroxy-3-tert-butylphenyl]butyric acid]glycol ester,4,4′-butylidenebis(6-tert-butyl-m-cresol),1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane,bis[2-tert-butyl-4-methyl-6-(2-hydroxy-3-tert-butyl-5-methylbenzyl)phenyl]terephthalate,1,3,5-tris(2,6-dimethyl-3-hydroxy-4-tert-butyl)benzylisocyanurate,1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene,tetrakis[methylene-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]methane,1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate,1,3,5-tris[(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxyethyl]isocyanurate,2-octylthio-4,6-di(4-hydroxy-3,5-di-tert-butyl)phenoxy-1,3,5-triazineand 4,4′-thiobis(6-tert-butyl-m-cresol); and polyhydric phenol/carbonicacid oligoesters, such as carbonic acid oligoesters (e.g.,polymerization degrees of 2 to 10) of4,4′-butylidenebis(2-tert-butyl-5-methylphenol).

The sulfur-based antioxidants include dialkyl thiodipropionates such asdilauryl, dimyristyl and distearyl thiodipropionates; and esters (forexample, pentaerythritoltetralauryl thiopropionate) formed between alkylthiopropionic acids such as butyl, octyl, lauryl and stearylthiopropionic acids and polyhydric alcohols such as glycerol,trimethylolethane, trimethylolpropane, pentaerythritol andtrishydroxyethyl isocyanurate.

The phosphorous-based antioxidants include trioctyl phosphite, trilaurylphosphite, tridecyl phosphite, octyl-diphenyl phosphite,tris(2,4-di-tert-butylphenyl)phosphite, triphenyl phosphite,tris(butoxyethyl)phosphite, tris(nonylphenyl)phosphite,distearylpentaerythritol diphosphite, tetra(tridecyl)-1,1,3-tris(2-methyl-5-tert-butyl-4-hydroxyphenyl)butane diphosphite, tetra(C₁₂₋₁₅alkyls)-4,4′-isopropylidenediphenyl diphosphite,tetra(tridecyl)-4,4′-butylidenebis(3-methyl-6-tert-butylphenol)diphosphite,tris(3,5-di-tert-butyl-4-hydroxyphenyl)phosphite, tris(mono- anddi-nonylphenyls) phosphite, hydrogenated-4,4′-isopropylidenediphenolpolyphosphite,bis(octylphenyl).bis[4,4′-butylidenebis(3-methyl-6-tert-butylphenol)].1,6-hexanedioldiphosphite, phenyl.4,4′-isopropylidenediphenol.pentaerythritoldiphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite,bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite,tris[4,4′-isopropylidenebis(2-tert-butylphenol)]phosphite,phenyl.diisodecyl phosphite, di(nonylphenyl)pentaerythritol diphosphite,tris(1,3-di-stearoyloxyisopropyl)phosphite,4,4′-isopropylidenebis(2-tert-butylphenol).di(nonylphenyl)phosphite,9,10-di-hydro-9-oxa-9-oxa-10-phosphaphenanthrene-10-oxide andtetrakis(2,4-di-tert-butylphenyl)-4,4′-biphenylene diphosphonite.

Other antioxidants include 6-hydroxychromane derivatives, such as α-,β-, γ- and δ-tocopherols and mixtures thereof, 2,5-dimethyl substitutionproduct, 2,5,8-trimethyl substitution product and 2,5,7,8-tetramethylsubstitution product of 2-(4-methyl-penta-3-enyl)-6-hydroxychroman,2,2,7-trimethyl-5-tert-butyl-6-hydroxychroman,2,2,5-trimethyl-7-tert-butyl-6-hydroxychroman,2,2,5-trimethyl-6-tert-butyl-6-hydroxychroman and2,2-dimethyl-5-tert-butyl-6-hydroxychroman.

Exemplary hydrochloric acid absorbers include double compoundsrepresented by M_(x)Al_(y)(OH)_(2x+3y−2z)(A)_(z).aH₂O (wherein M is Mg,Ca or Zn; A is an anion other then the hydroxyl group; x, y and z areeach a positive number; and a is 0 or a positive number), such asMg₆Al₂(OH)₁₆CO₃.4H₂O, Mg₆Al₂(OH)₂₀CO₃.5H₂O, Mg₅Al₂(OH)₁₄CO₃.4H₂O,Mg₁₀Al₂(OH)₂₂(CO₃)₂.4H₂O, Mg₆Al₂(OH)₁₆HPO₄.4H₂O, Ca₆Al₂(OH)₁₆CO₃.4H₂O,Zn₆Al₂(OH)₁₆CO₃.4H₂O, Zn₆Al₂(OH)₁₆SO₄.4H₂O, Mg₆Al₂(OH)₁₆SO₃.4H₂O andMg₆Al₂(OH)₁₂CO₃.3H₂O.

The light stabilizers include hydroxybenzophenones, such as2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone,2,2′-di-hydroxy-4-methoxybenzophenone and 2,4-dihydroxybenzophenone;benzotriazoles, such as2-(2′-hydroxy-3′-tert-butyl-5′-methylphenyl)-5-chlorobenzotriazole,2-(2′-hydroxy-3′,5′-di-tert-butylphenyl)-5-chlorobenzotriazole,2-(2′-hydroxy-5′-methylphenyl)benzotriazole and2-(2′-hydroxy-3′,5′-di-tert-amylphenyl)benzotriazole; benzoates, such asphenyl salicylate, p-tert-butylphenyl salicylate,2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate andhexadecyl-3,5-di-tert-butyl-4-hydroxybenzoate; nickel compounds, such as2,2′-thiobis(4-tert-octylphenol) nickelate,[2,2′-thiobis(4-tert-octylphenolato)]-n-butylamine nickelate and(3,5-di-tert-butyl-4-hydroxybenzyl)monoethyl phosphonate nickelate;substituted acrylonitriles, such asα-cyano-β-methyl-β-(p-methoxyphenyl)methyl acrylate; oxalic aciddiamides, such as N′-2-ethylphenyl-N-ethoxy-5-tert-butylphenyloxalicdiamide and N-2-ethylphenyl-N′-2-ethoxyphenyloxalic diamide; andhindered amine compounds, such asbis(2,2,6,6-tetramethyl-4-piperidine)sebacate,poly[{(6-(1,1,3,3-tetramethylbutyl)imino}-1,3,5-triadine-2,4-diyl{4-(2,2,6,6-tetramethylpiperidyl)imino}hexamethylene]and a condensate of 2-(4-hydroxy-2,2,6,6-tetramethyl-1-piperidyl)ethanoland dimethyl succinate.

The lubricants include aliphatic hydrocarbons, such as paraffin waxes,polyethylene waxes and polypropylene waxes; higher fatty acids, such ascapric acid, lauric acid, myristic acid, palmitic acid, margaric acid,stearic acid, arachidic acid and behenic acid, and metal salts thereof,such as lithium salts, calcium salts, sodium salts, magnesium salt andpotassium salts thereof; aliphatic alcohols, such as palmityl alcohols,cetyl alcohols and stearyl alcohols; aliphatic amides, such as caproicamides, caprylic amides, capric amides, lauric amides, myristic amides,palmitic amides, stearic amides and erucic amides; esters of aliphaticcompounds and alcohols; and fluorine compounds, such asfluoroalkylcarboxylic acids, metal salts thereof and metal salts offluoroalkylsulfonic acids.

The anti-blocking agents include fine particles of inorganic compounds,such as silica, alumina, alumina silicate and diatomaceous earth; andfine particles of organic compounds, such as polyethylenes, crosslinkedpolyethylenes, polymethyl methacrylates and crosslinked polymethylmethacrylates.

The polypropylene composition may contain these additives in amountsbetween 0.0001 and 10 wt %. These additives enable the polypropylenecomposition of the present invention to provide molded articles thathave further improved property balance, durability, paintability,printability, scratch resistance and molding processability.

As described earlier, the polypropylene composition of the presentinvention may contain a nucleating agent. Herein, various nucleatingagents known in the art may be used without limitation. Particularly,aromatic phosphates, dibenzylidene sorbitols and other nucleating agentsgiven below are preferable nucleating agents.

In the formula immediately above, R¹ is an oxygen atom, a sulfur atom ora hydrocarbon group of 1 to 10 carbon atoms; R² and R³, which may be thesame or different, are each a hydrogen atom or a hydrocarbon group of 1to 10 carbon atoms; R², R³'s, or R² and R³ may link together to form aring; M is a metal atom having a valency of 1 to 3; and n is an integerof 1 to 3.

The nucleating agents having this formula includesodium-2,2′-methylene-bis(4,6-di-t-butylphenyl)phosphate,sodium-2,2′-ethylidene-bis(4,6-di-t-butylphenyl)phosphate,lithium-2,2′-methylene-bis(4,6-di-t-butylphenyl)phosphate,lithium-2,2′-ethylidene-bis(4,6-di-t-butylphenyl)phosphate,sodium-2,2′-ethylidene-bis(4-i-propyl-6-t-butylphenyl)phosphate,lithium-2,2′-methylene-bis(4-methyl-6-t-butylphenyl)phosphate,lithium-2,2′-methylene-bis(4-ethyl-6-t-butylphenyl)phosphate,calcium-bis[2,2′-thiobis (4-methyl-6-t-butylphenyl)phosphate],calcium-bis[2,2′-thiobis(4-ethyl-6-t-butylphenyl)phosphate],calcium-bis[2,2′-thiobis-(4,6-di-t-butylphenyl)phosphate],magnesium-bis[2,2′-thiobis(4,6-di-t-butylphenyl)phosphate],magnesium-bis[2,2′-thiobis-(4-t-octylphenyl)phosphate],sodium-2,2′-butylidene-bis(4,6-di-methylphenyl)phosphate,sodium-2,2′-butylidene-bis(4,6-di-t-butylphenyl)phosphate,sodium-2,2′-t-octylmethylene-bis(4,6-di-methylphenyl)phosphate,sodium-2,2′-t-octylmethylene-bis(4,6-di-t-butylphenyl)phosphate,calcium-bis-(2,2′-methylene-bis(4,6-di-t-butylphenyl)phosphate),magnesium-bis[2,2′-methylene-bis(4,6-di-t-butylphenyl)phosphate],barium-bis[2,2′-methylene-bis(4,6-di-t-butylphenyl)phosphate],sodium-2,2′-methylene-bis(4-methyl-6-t-butylphenyl)phosphate,sodium-2,2′-methylene-bis(4-ethyl-6-t-butylphenyl)phosphate,sodium(4,4′-dimethyl-5,6′-di-t-butyl-2,2′-biphenyl)phosphate,calcium-bis[(4,4′-dimethyl-6,6′-di-t-butyl-2,2′-biphenyl)phosphate],sodium-2,2′-ethylidene-bis(4-m-butyl-6-t-butylphenyl)phosphate,sodium-2,2′-methylene-bis(4,6-di-methylphenyl)phosphate,sodium-2,2′-methylene-bis (4,6-di-ethylphenyl)phosphate,potassium-2,2′-ethylidene-bis(4,6-di-t-butylphenyl)phosphate,calcium-bis[2,2′-ethylidene-bis(4,6-di-t-butylphenyl)phosphate],magnesium-bis[2,2′-ethylidene-bis(4,6-di-t-butylphenyl)phosphate],barium-bis[2,2′-ethylidene-bis(4,6-di-t-butylphenyl)phosphate],aluminum-tris[2,2′-methylene-bis(4,6-di-t-butylphenyl)phosphate],aluminum-tris[2,2′-ethylidene-bis(4,6-di-t-butylphenyl)phosphate] andmixtures thereof. Of these,sodium-2,2′-methylene-bis(4,6-di-t-butylphenyl)phosphate is preferable.

In the formula immediately above, R⁴ is a hydrogen atom or a hydrocarbongroup of 1 to 10 carbon atoms; M is a metal atom having a valency of 1to 3; and n is an integer of 1 to 3.

The nucleating agents having this formula includesodium-bis(4-t-butylphenyl)phosphate,sodium-bis(4-methylphenyl)phosphate, sodium-bis(4-ethylphenyl)phosphate,sodium-bis(4-i-propylphenyl)phosphate,sodium-bis(4-t-octylphenyl)phosphate,potassium-bis(4-t-butylphenyl)phosphate,calcium-bis(4-t-butylphenyl)phosphate,magnesium-bis(4-t-butylphenyl)phosphate,lithium-bis(4-t-butylphenyl)phosphate,aluminum-bis(4-t-butylphenyl)phosphate, and mixtures thereof. Of these,sodium-bis(4-t-butylphenyl)phosphate is preferable.

In the formula immediately above, each R⁵ is a hydrogen atom or ahydrocarbon group of 1 to 10 carbon atoms.

The nucleating agents having this formula include 1,3,2,4-dibenzylidenesorbitol, 1,3-benzylidene-2,4-p-methylbenzylidene sorbitol,1,3-benzylidene-2,4-p-ethylbenzylidene sorbitol,1,3-p-methylbenzylidene-2,4-benzylidene sorbitol,1,3-p-ethylbenzylidene-2,4-benzylidene sorbitol,1,3-p-methylbenzylidene-2,4-p-ethylbenzylidene sorbitol,1,3-p-ethylbenzylidene-2,4-p-methylbenzylidene sorbitol,1,3,2,4-di(p-methylbenzylidene)sorbitol,1,3,2,4-di(p-ethylbenzylidene)sorbitol,1,3,2,4-di(p-n-propylbenzylidene)sorbitol,1,3,2,4-di(p-i-propylbenzylidene)sorbitol,1,3,2,4-di(p-n-butylbenzylidene)sorbitol,1,3,2,4-di(p-s-butylbenzylidene)sorbitol,1,3,2,4-di(p-t-butylbenzylidene)sorbitol,1,3,2,4-di(2′,4′-dimethylbenzylidene)sorbitol,1,3,2,4-di(p-methoxybenzylidene)sorbitol,1,3,2,4-di(p-ethoxybenzylidene)sorbitol,1,3-benzylidene-2-4-p-chlorobenzylidene sorbitol,1,3-p-chlorobenzylidene-2,4-benzylidene sorbitol,1,3-p-chlorobenzylidene-2,4-p-methylbenzylidene sorbitol,1,3-p-chlorobenzylidene-2,4-p-ethylbenzylidene sorbitol,1,3-p-methylbenzylidene-2,4-p-chlorobenzylidene sorbitol,1,3-p-ethylbenzylidene-2,4-p-chlorobenzylidene sorbitol,1,3,2,4-di(p-chlorobenzylidene)sorbitol and mixtures thereof. Of these,1,3,2,4-dibenzylidene sorbitol, 1,3,2,4-di(p-methylbenzylidene)sorbitol,1,3,2,4-di(p-ethylbenzylidene)sorbitol,1,3-p-chlorobenzylidene-2,4-p-methylbenzylidene sorbitol,1,3,2,4-di(p-chlorobenzylidene)sorbitol and mixtures thereof arepreferable.

Other nucleating agents include metallic salts of aromatic carboxylicacids and of aliphatic carboxylic acids, such as aluminum benzoate,aluminum p-t-butylbenzoate, sodium adipate, sodium thiophenecarboxylateand sodium pyrrolecarboxylate.

Inorganic compounds such as talc are also employable as the nucleatingagents. The polypropylene compositions (CC-1) and (CC-2) may eachcontain the nucleating agent in an amount of 0.001 to 10 wt %,preferably 0.01 to 5 wt %, and particularly preferably 0.1 to 3 wt %.

Examples of the other resins include thermoplastic resins andthermosetting resins, including α-olefin homopolymers such aspolyethylene and poly-1-butene, α-olefin copolymers, copolymers ofα-olefins and vinyl monomers, modified olefin polymers such as maleicanhydride-modified polypropylenes, nylons, polycarbonates, ABS resins,polystyrenes, polyvinyl chlorides, polyphenylene oxides, petroleumresins and phenolic resins.

Further, the polypropylene compositions (CC-1) and (CC-2) of the presentinvention may each contain an inorganic filler. Examples thereofinclude:

powdery fillers, including natural silicic acids and silicates such asfine powder talc, kaolinite, calcined clay, pyrophyllite, sericite andwollastonite; carbonates such as precipitated calcium carbonate, groundcalcium carbonate and magnesium carbonate; hydroxides such as aluminumhydroxide and magnesium hydroxide; oxides such as zinc oxide, zinc whiteand magnesium oxide; and synthetic silicic acids and silicates such ashydrated calcium silicate, hydrated aluminum silicate, hydrated silicicacid and silicic anhydride;

flaky fillers, including mica;

fibrous fillers, including basic magnesium sulfate whisker, calciumtitanate whisker, aluminum borate whisker, sepiolite, PMF (processedmineral fiber), xonotlite, potassium titanate and ellestadite; and

balloon fillers, including glass balloon and fly ash balloon.

Of these fillers, fine powder talc is preferably used in the presentinvention. Particularly preferably, the fine powder talc has a meanparticle diameter of 0.2 to 3 μm, especially 0.2 to 2.5 μm.

Desirably, the fine powder talc contains particles whose mean diameteris 5 μm or more in an amount of 10 wt % or less, preferably 8 wt % orless. The mean particle diameter of the talc can be measured byliquid-phase precipitation.

The talc for use in the present invention preferably has a mean aspectratio (ratio of longitudinal or lateral length to thickness) of 3 ormore, particularly 4 or more.

The inorganic fillers of the present invention, particularly talc, maybe surface treated prior to use, which is not compulsory. The surfacetreatment can be carried out chemically, for example, using treatingagents such as silane coupling agents, higher fatty acids, metal saltsof fatty acids, unsaturated organic acids, organic titanates, resinacids and polyethylene glycols or physically.

The surface-treated inorganic fillers, such as talc, enable thepolypropylene composition to exhibit excellent weld strength,paintability and molding processability.

The inorganic fillers as mentioned above may be used in combination oftwo or more kinds. If necessary, in the present invention, organicfillers such as high styrenes, lignins and reclaimed rubbers may be usedtogether with the inorganic fillers.

The polypropylene composition (CC-1) of the present invention exhibitsexcellent heat resistance and low-temperature heat-sealability as wellas adequate flexibility and impact resistance. The polypropylenecomposition may be favorably used to produce, in addition to the sheetor film as disclosed in the present invention, injection molded articlessuch as containers, stretch-blow molded articles and containers forretort pouch foods that have improved impact resistance.

The polypropylene composition (CC-1) of the present invention has othervarious applications, including home electric appliance parts such ashousings and washing machine tubs; automobile interior parts such astrims, interior panels and column covers; automobile exterior parts suchas fenders, bumpers, side moles, mudguards and mirror covers; andordinary miscellaneous goods.

The propylene/1-butene random copolymer (PBR) described above may bepartially or completely modified with an unsaturated carboxylic acid oran anhydride thereof. The modified propylene/1-butene random copolymercan exhibit enhanced overlap packaging properties and adhesion tometals.

The sheet or film obtained from the polypropylene composition accordingto the present invention has a thickness of 1 to 2000 μm, preferably 2to 1500 μm.

The sheet or film obtainable from the polypropylene composition exhibitsexcellent flexibility, impact resistance, transparency, low-temperatureheat-sealability, anti-blocking properties, and mechanical strength suchas scratch resistance. Therefore, it can be suitably employed astransparent and flexible sheets, and as sealant films.

The sheet or film of the present invention may be produced by the knownproduction method for polyolefin sheets or films. Exemplary processesinclude extrusion, such as cast film extrusion and inflation filmextrusion, and calendering. Since the polypropylene composition of thepresent invention has an excellent balance between the melting point andthe crystallization rate, it can provide sheets or films having goodappearance by the above processes with good productivity.

The laminate according to the present invention comprises a crystallinepolypropylene layer (I) and a polypropylene resin composition layer (II)disposed on at least one surface of the crystalline polypropylene layer(I). The crystalline polypropylene layer (I) ranges in thickness from 1to 2000 μm, preferably from 2 to 1500 μm, and the polypropylenecomposition layer (II) has a thickness of 0.1 to 200 μm, preferably 0.2to 150 μm.

The laminate of the present invention has excellent transparency,low-temperature heat-sealability, anti-blocking properties, andmechanical strength such as scratch resistance. Therefore, it can besuitably employed as sealant films.

The laminate of the present invention may be produced by the knownproduction process for polyolefin laminates. Preferred processes includecoextrusion. Since the polypropylene composition of the presentinvention has an excellent balance between the melting point and thecrystallization rate, it can provide sheets or films having goodappearance by the above process with good productivity.

The sheet, film or laminate (otherwise composite film) according to thepresent invention may be unoriented or oriented in at least onedirection. The unoriented or oriented sheet or film may be coronatreated on either or both surfaces by the conventional method.

The oriented film may be favorably used as sealant films and shrinkfilms. Particularly, the oriented film obtainable from the polypropylenecomposition of the present invention is ideal as a shrink film becauseof its excellent shrink properties. Orientation may be carried out byconventional methods for stretching polyolefin films. Specific examplesinclude rolling orientation, tentering and tubular orientation. The drawratio is 1.5 to 30 times, and generally 3 to 15 times.

The sheet, film, laminate, oriented film and oriented laminate of thepresent invention may be used singly or, for the purpose of higherbarrier properties and rigidity, may be laminated with another film. Thelaminating films include polyolefin films, polystyrene films, polyesterfilms, polyamide films, oriented films thereof, laminates of polyolefinfilms and gas-barrier films, aluminum foils, paper and metallized films.Preferred laminating processes include extrusion laminating and drylaminating.

The sheet, film and laminate comprising the polypropylene composition ofthe present invention have excellent transparency, flexibility,anti-blocking properties and heat-sealability. Particularly, they can beheat sealed even at lower temperatures to provide a wide range of heatseal temperatures. Also, they can be heat sealed with sufficientstrength. The film remains unchanged in terms of heat seal strength evenafter long storage, so that stable heat sealing is ensured. The filmobtained by orienting the sheet, film or laminate according to thepresent invention exhibits superior heat sealability, blockingresistance and shrink properties.

The sheet, film, laminate, oriented film and oriented laminate(otherwise composite film) of the present invention have exceptionaltransparency, scratch resistance and blocking resistance to allowhigh-speed packaging. Therefore, they are favorably used in, forexample, food packaging, packed wrapping and fiber packaging.

Hereinbelow, descriptions will be sequentially presented for thetransition metal compound of the formula (2a), exemplary preferredtransition metal compounds, production process for the transition metalcompound, preferred embodiment of the transition metal compound inolefin polymerization catalysts, and olefin polymerization in thepresence of an olefin polymerization catalyst containing the transitionmetal compound of the present invention.

Transition metal compound

The transition metal compound according to the present invention has theformula (2a):

wherein R¹ and R³ are each a hydrogen atom; R² and R⁴, which may be thesame or different, are each a hydrocarbon group or a silicon-containinggroup; and R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹² and R¹³, which may be thesame or different, are each a hydrogen atom, a hydrocarbon group or asilicon-containing group.

The hydrocarbon groups include linear hydrocarbon groups such as methyl,ethyl, n-propyl, allyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl,n-nonyl and n-decanyl groups; branched hydrocarbon groups such asisopropyl, tert-butyl, amyl, 3-methylpentyl, 1,1-diethylpropyl,1,1-dimethylbutyl, 1-methyl-1-propylbutyl, 1,1-dipropylbutyl,1,1-dimethyl-2-methylpropyl and 1-methyl-1-isopropyl-2-methylpropylgroups; saturated cyclic hydrocarbon groups such as cyclopentyl,cyclohexyl, cycloheptyl, cyclooctyl, norbornyl and adamantyl groups;unsaturated cyclic hydrocarbon groups such as phenyl, tolyl, naphthyl,biphenyl, phenanthryl and anthracenyl groups; saturated hydrocarbongroups substituted with unsaturated cyclic hydrocarbon groups, such asbenzyl, cumyl, 1,1-diphenylethyl and triphenylmethyl groups; andheteroatom-containing hydrocarbon groups such as methoxy, ethoxy,phenoxy, furyl, N-methylamino, N,N-dimethylamino, N-phenylamino, pyrryland thienyl groups.

The silicon-containing groups include trimethylsilyl, triethylsilyl,dimethylphenylsilyl, diphenylmethylsilyl and triphenylsilyl groups.Neighboring substituent groups of R⁵ to R¹² may link together to form aring. Examples of the substituted fluorenyl group includebenzofluorenyl, dibenzofluorenyl, octahydrodibenzofluorenyl,octamethyloctahydrodibenzofluorenyl andoctamethyltetrahydrodicyclopentafluorenyl groups.

R¹⁴ is an aryl group. Examples thereof include the above-mentionedunsaturated cyclic hydrocarbon groups, saturated hydrocarbon groupssubstituted with unsaturated cyclic hydrocarbon groups, andheteroatom-containing unsaturated cyclic hydrocarbon groups such asfuryl, pyrryl and thienyl groups. R¹³ and R¹⁴ may be the same ordifferent and may link together to form a ring. Examples of suchsubstituent groups include:

In the formula (2a), R² and R⁴, substituent groups to thecyclopentadienyl ring, are preferably hydrocarbon groups of 1 to 20carbon atoms. Examples of the hydrocarbon groups of 1 to 20 carbon atomsinclude the aforementioned hydrocarbon groups. More preferably, R² is abulky substituent group such as tert-butyl, adamantyl or triphenylmethylgroup, and R⁴ is a sterically smaller substituent group than R², such asmethyl, ethyl or n-propyl group. As used herein, “sterically smaller”means that the substituent group has a smaller volume.

Of the substituent groups R⁵ to R¹² to the fluorenyl rings in theformula (2a), arbitrary two or more groups of R⁶, R⁷, R¹⁰ and R¹¹ arepreferably hydrocarbon groups of 1 to 20 carbon atoms. Examples of thehydrocarbon groups of 1 to 20 carbon atoms include the aforesaidhydrocarbon groups. For the purpose of easy synthesis of a ligand, thesegroups are preferably symmetrical: R⁶ and R¹¹ are the same groups and R⁷and R¹⁰ are the same groups. In one of such preferred embodiments, R⁶and R⁷ form an aliphatic ring (AR-1) and R¹⁰ and R¹¹ form an aliphaticring (AR-2) identical to the aliphatic ring (AR-1).

Referring to the formula (2a), Y bridging the cyclopentadienyl andfluorenyl rings is a carbon atom. The substituent groups R¹³ and R¹⁴ toY are preferably both aryl groups having 6 to 20 carbon atoms. Thesesubstituent groups may be the same or different, and may link togetherto form a ring. Exemplary aryl groups of 6 to 20 carbon atoms includethe above-mentioned unsaturated cyclic hydrocarbon groups, saturatedhydrocarbon groups substituted with unsaturated cyclic hydrocarbongroups, and heteroatom-containing unsaturated cyclic hydrocarbon groups.R¹³ and R¹⁴ may be the same or different, and may link together to forma ring. Preferred examples thereof include fluorenylidene,10-hydroanthracenylidene and dibenzocycloheptadienylidene groups.

In the formula (2a), M denotes a Group-4 transition metal, such as Ti,Zr or Hf; Q denotes a halogen atom, a hydrocarbon group, an anionicligand or a neutral ligand capable of coordination by a lone pair ofelectrons, and may be the same or different when plural; and j is aninteger of 1 to 4. When j is 2 or greater, Q may be the same ordifferent. The halogens include fluorine, chlorine, bromine and iodine.Examples of the hydrocarbon group are as described above. Exemplaryanionic ligands include alkoxy groups such as methoxy, tert-butoxy andphenoxy groups; carboxylate groups such as acetate and benzoate groups;and sulfonate groups such as mesylate and tosylate groups. The neutralligands capable of coordination by a lone pair of electrons includeorganophosphorus compounds such as trimethylphosphine,triethylphosphine, triphenylphosphine and diphenylmethylphosphine; andethers such as tetrahydrofuran, diethylether, dioxane and1,2-dimethoxyethane. Preferably, at least one Q is the halogen atom oralkyl group.

Exemplary Preferred Transition Metal Compounds

Preferred transition metal compounds for the present invention includediphenylmethylene(3,5-dimethyl-cyclopentadienyl)(fluorenyl)zirconiumdichloride,diphenylmethylene(3,5-dimethyl-cyclopentadienyl)(2,7-di-tert-butylfluorenyl)zirconiumdichloride,diphenylmethylene(3,5-dimethyl-cyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirconiumdichloride,diphenylmethylene(3,5-dimethyl-cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)zirconiumdichloride,diphenylmethylene(3-tert-butyl-5-methyl-cyclopentadienyl)(fluorenyl)zirconiumdichloride,diphenylmethylene(3-tert-butyl-5-methyl-cyclopentadienyl)(2,7-di-tert-butylfluorenyl)zirconiumdichloride,diphenylmethylene(3-tert-butyl-5-methyl-cyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirconiumdichloride,diphenylmethylene(3-tert-butyl-5-methyl-cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)zirconiumdichloride,diphenylmethylene(3-(2-adamantyl)-5-methyl-cyclopentadienyl)(fluorenyl)zirconiumdichloride,diphenylmethylene(3-(2-adamantyl)-5-methyl-cyclopentadienyl)(2,7-di-tert-butylfluorenyl)zirconiumdichloride,diphenylmethylene(3-(2-adamantyl)-5-methyl-cyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirconiumdichloride,diphenylmethylene(3-(2-adamantyl)-5-methyl-cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)zirconiumdichloride,diphenylmethylene(3-tert-butyl-5-ethyl-cyclopentadienyl)(fluorenyl)zirconiumdichloride,diphenylmethylene(3-tert-butyl-5-ethyl-cyclopentadienyl)(2,7-di-tert-butylfluorenyl)zirconiumdichloride,diphenylmethylene(3-tert-butyl-5-ethyl-cyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirconiumdichloride,diphenylmethylene(3-tert-butyl-5-ethyl-cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)zirconiumdichloride,diphenylmethylene(3-tert-butyl-2,5-dimethyl-cyclopentadienyl)(fluorenyl)zirconiumdichloride,diphenylmethylene(3-tert-butyl-2,5-dimethyl-cyclopentadienyl)(2,7-di-tert-butylfluorenyl)zirconiumdichloride,diphenylmethylene(3-tert-butyl-2,5-dimethyl-cyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirconiumdichloride,diphenylmethylene(3-tert-butyl-2,5-dimethyl-cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)zirconiumdichloride,di(p-tolyl)methylene(3,5-dimethyl-cyclopentadienyl)(fluorenyl)zirconiumdichloride,di(p-tolyl)methylene(3,5-dimethyl-cyclopentadienyl)(2,7-di-tert-butylfluorenyl)zirconiumdichloride,di(p-tolyl)methylene(3,5-dimethyl-cyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirconiumdichloride,di(p-tolyl)methylene(3,5-dimethyl-cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)zirconiumdichloride,di(p-tolyl)methylene(3-tert-butyl-5-methyl-cyclopentadienyl)(fluorenyl)zirconiumdichloride,di(p-tolyl)methylene(3-tert-butyl-5-methyl-cyclopentadienyl)(2,7-di-tert-butylfluorenyl)zirconiumdichloride,di(p-tolyl)methylene(3-tert-butyl-5-methyl-cyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirconiumdichloride,di(p-tolyl)methylene(3-tert-butyl-5-methyl-cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)zirconiumdichloride,di(p-tolyl)methylene(3-(2-adamantyl)-5-methyl-cyclopentadienyl)(fluorenyl)zirconiumdichloride,di(p-tolyl)methylene(3-(2-adamantyl)-5-methyl-cyclopentadienyl)(2,7-di-tert-butylfluorenyl)zirconiumdichloride,di(p-tolyl)methylene(3-(2-adamantyl)-5-methyl-cyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirconiumdichloride,di(p-tolyl)methylene(3-(2-adamantyl)-5-methyl-cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)zirconiumdichloride,di(p-tolyl)methylene(3-tert-butyl-5-ethyl-cyclopentadienyl)(fluorenyl)zirconiumdichloride,di(p-tolyl)methylene(3-tert-butyl-5-ethyl-cyclopentadienyl)(2,7-di-tert-butylfluorenyl)zirconiumdichloride,di(p-tolyl)methylene(3-tert-butyl-5-ethyl-cyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirconiumdichloride,di(p-tolyl)methylene(3-tert-butyl-5-ethyl-cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)zirconiumdichloride,di(p-tolyl)methylene(3-tert-butyl-2,5-dimethyl-cyclopentadienyl)(fluorenyl)zirconiumdichloride,di(p-tolyl)methylene(3-tert-butyl-2,5-dimethyl-cyclopentadienyl)(2,7-di-tert-butylfluorenyl)zirconiumdichloride,di(p-tolyl)methylene(3-tert-butyl-2,5-dimethyl-cyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirconiumdichloride,di(p-tolyl)methylene(3-tert-butyl-2,5-dimethyl-cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)zirconiumdichloride,di(p-tert-butylphenyl)methylene(3,5-dimethyl-cyclopentadienyl)(fluorenyl)zirconiumdichloride,di(p-tert-butylphenyl)methylene(3,5-dimethyl-cyclopentadienyl)(2,7-di-tert-butylfluorenyl)zirconiumdichloride,di(p-tert-butylphenyl)methylene(3,5-dimethyl-cyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirconiumdichloride,di(p-tert-butylphenyl)methylene(3,5-dimethyl-cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)zirconiumdichloride,di(p-tert-butylphenyl)methylene(3-tert-butyl-5-methyl-cyclopentadienyl)(fluorenyl)zirconiumdichloride,di(p-tert-butylphenyl)methylene(3-tert-butyl-5-methyl-cyclopentadienyl)(2,7-di-tert-butylfluorenyl)zirconiumdichloride,di(p-tert-butylphenyl)methylene(3-tert-butyl-5-methyl-cyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirconiumdichloride,di(p-tert-butylphenyl)methylene(3-tert-butyl-5-methyl-cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)zirconiumdichloride,di(p-tert-butylphenyl)methylene(3-(2-adamantyl)-5-methyl-cyclopentadienyl)(fluorenyl)zirconiumdichloride,di(p-tert-butylphenyl)methylene(3-(2-adamantyl)-5-methyl-cyclopentadienyl)(2,7-di-tert-butylfluorenyl)zirconiumdichloride,di(p-tert-butylphenyl)methylene(3-(2-adamantyl)-5-methyl-cyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirconiumdichloride,di(p-tert-butylphenyl)methylene(3-(2-adamantyl)-5-methyl-cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)zirconiumdichloride,di(p-tert-butylphenyl)methylene(3-tert-butyl-5-ethyl-cyclopentadienyl)(fluorenyl)zirconiumdichloride,di(p-tert-butylphenyl)methylene(3-tert-butyl-5-ethyl-cyclopentadienyl)(2,7-di-tert-butylfluorenyl)zirconiumdichloride,di(p-tert-butylphenyl)methylene(3-tert-butyl-5-ethyl-cyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirconiumdichloride,di(p-tert-butylphenyl)methylene(3-tert-butyl-5-ethyl-cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)zirconiumdichloride,di(p-tert-butylphenyl)methylene(3-tert-butyl-2,5-dimethyl-cyclopentadienyl)(fluorenyl)zirconiumdichloride,di(p-tert-butylphenyl)methylene(3-tert-butyl-2,5-dimethyl-cyclopentadienyl)(2,7-di-tert-butylfluorenyl)zirconiumdichloride,di(p-tert-butylphenyl)methylene(3-tert-butyl-2,5-dimethyl-cyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirconiumdichloride,di(p-tert-butylphenyl)methylene(3-tert-butyl-2,5-dimethyl-cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)zirconiumdichloride,(methyl)(phenyl)methylene(3-tert-butyl-5-methyl-cyclopentadienyl)(fluorenyl)zirconiumdichloride,(methyl)(phenyl)methylene(3-tert-butyl-5-methyl-cyclopentadienyl)(2,7-di-tert-butylfluorenyl)zirconiumdichloride,(methyl)(phenyl)methylene(3-tert-butyl-5-methyl-cyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirconiumdichloride,(methyl)(phenyl)methylene(3-tert-butyl-5-methyl-cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)zirconium dichloride,(p-tolyl)(phenyl)methylene(3-tert-butyl-5-methyl-cyclopentadienyl)(fluorenyl)zirconiumdichloride,(p-tolyl)(phenyl)methylene(3-tert-butyl-5-methyl-cyclopentadienyl)(2,7-di-tert-butylfluorenyl)zirconiumdichloride,(p-tolyl)(phenyl)methylene(3-tert-butyl-5-methyl-cyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirconiumdichloride,(p-tolyl)(phenyl)methylene(3-tert-butyl-5-methyl-cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)zirconiumdichloride,dibenzylmethylene(3-tert-butyl-5-methyl-cyclopentadienyl)(fluorenyl)zirconiumdichloride,dibenzylmethylene(3-tert-butyl-5-methyl-cyclopentadienyl)(2,7-di-tert-butylfluorenyl)zirconiumdichloride,dibenzylmethylene(3-tert-butyl-5-methyl-cyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirconiumdichloride,dibenzylmethylene(3-tert-butyl-5-methyl-cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)zirconiumdichloride,fluorenylidene(3-tert-butyl-5-methyl-cyclopentadienyl)(fluorenyl)zirconiumdichloride,fluorenylidene(3-tert-butyl-5-methyl-cyclopentadienyl)(2,7-di-tert-butylfluorenyl)zirconiumdichloride,fluorenylidene(3-tert-butyl-5-methyl-cyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirconiumdichloride,fluorenylidene(3-tert-butyl-5-methyl-cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)zirconiumdichloride,diphenylmethylene(3-tert-butyl-5-methyl-cyclopentadienyl)(fluorenyl)zirconiumdimethyl,diphenylmethylene(3-tert-butyl-5-methyl-cyclopentadienyl)(2,7-di-tert-butylfluorenyl)zirconiumdimethyl,diphenylmethylene(3-tert-butyl-5-methyl-cyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirconiumdimethyl,diphenylmethylene(3-tert-butyl-5-methyl-cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)zirconiumdimethyl,diphenylmethylene(3-tert-butyl-5-methyl-cyclopentadienyl)(fluorenyl)titaniumdichloride,diphenylmethylene(3-tert-butyl-5-methyl-cyclopentadienyl)(2,7-di-tert-butylfluorenyl)titaniumdichloride,diphenylmethylene(3-tert-butyl-5-methyl-cyclopentadienyl)(3,6-di-tert-butylfluorenyl)titaniumdichloride,diphenylmethylene(3-tert-butyl-5-methyl-cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)titaniumdichloride,diphenylmethylene(3-tert-butyl-5-methyl-cyclopentadienyl)(fluorenyl)hafniumdichloride,diphenylmethylene(3-tert-butyl-5-methyl-cyclopentadienyl)(2,7-di-tert-butylfluorenyl)hafniumdichloride,diphenylmethylene(3-tert-butyl-5-methyl-cyclopentadienyl)(3,6-di-tert-butylfluorenyl)hafniumdichloride anddiphenylmethylene(3-tert-butyl-5-methyl-cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)hafniumdichloride. The transition metal compound of the present invention isnot limited to the above compounds, and all the compounds that can meetthe requirements specified in Claims are comprehended.

Production Process for the Transition Metal Compound

The transition metal compound, for example the compound of the formula(2a), may be synthesized as described below.

First, a precursor compound (1) of the compound represented by theformula (2a) is prepared by a series of steps [A] or [B] illustratedbelow:

wherein R¹ to R¹⁴ and Y are as defined for the formula (2a); L is analkali metal; Z¹ and Z², which may be the same or different, are each ahalogen or an anionic ligand; and (1), (2) and (5), which are shown withone exemplary form in the formulae, may be each an isomer different onlyin the positions of the double bonds in the cyclopentadienyl ring, or amixture of such isomers.

In the reaction process [A] or [B], the alkali metal used may belithium, sodium or potassium; the alkali earth metal may be magnesium orcalcium; the halogen may be fluorine, chlorine, bromine or iodine; andthe anionic ligand may be an alkoxy group such as methoxy, tert-butoxyor phenoxy, a carboxylate group such as acetate or benzoate, or asulfonate group such as mesylate or tosylate.

An exemplary process for the preparation of the metallocene compoundfrom the precursor compound (1) will be given below. The precursorcompound (1) obtained by the reaction process [A] or [B] is brought intocontact with an alkali metal, a hydrogenated alkali metal or anorganoalkali metal in an organic solvent at a reaction temperature of−80 to 200° C. to form a dialkali metal salt. Examples of the organicsolvent used herein include aliphatic hydrocarbons such as pentane,hexane, heptane, cyclohexane and decalin; aromatic hydrocarbons such asbenzene, toluene and xylene; ethers such as tetrahydrofuran,diethylether, dioxane and 1,2-dimethoxyethane; and halogenatedhydrocarbons such as dichloromethane and chloroform. Exemplary alkalimetals for use in the reaction include lithium, sodium and potassium;exemplary alkali metal hydrides include sodium hydride and potassiumhydride; and exemplary organoalkali metals include methyllithium,butyllithium and phenyllithium.

Thereafter, the dialkali metal salt resulting from the above contact isreacted in an organic solvent with a compound represented by the formula(11) below to give the metallocene compound of the formula (2a):MZ_(k)  (11)wherein M is a metal selected from Group 4 of the periodic table; Z is ahalogen, an anionic ligand or a neutral ligand capable of coordinationby a lone pair of electrons, and may be the same or different; and k isan integer of 3 to 6. Preferred compounds having the formula (11)include trivalent or tetravalent titanium fluorides, titanium chlorides,titanium bromides and titanium iodides; tetravalent zirconium fluorides,zirconium chlorides, zirconium bromides and zirconium iodides;tetravalent hafnium fluorides, hafnium chlorides, hafnium bromides andhafnium iodides; and complexes thereof with ethers such astetrahydrofuran, diethylether, dioxane and 1,2-dimethoxyethane. Theorganic solvent used herein is as described above. The reaction betweenthe dialkali metal salt and the compound of the formula (11) ispreferably an equimolar reaction and is carried out in the organicsolvent at a reaction temperature of −80 to 200° C. The resultantmetallocene compound may be isolated and purified by, for example,extraction, recrystallization and sublimation. Identification of thetransition metal compound of the present invention obtained as above canbe made by a proton NMR spectrum, a ¹³C-NMR spectrum, mass spectrometricanalysis and elemental analysis.Preferred Embodiment of the Transition Metal Compound in OlefinPolymerization Catalysts

A preferable embodiment of the transition metal compound of the presentinvention for use in an olefin polymerization catalyst will be givenbelow. When the transition metal compound of the present invention isused to form an olefin polymerization catalyst, catalyst componentspreferably comprise:

(A) the transition metal compound,

(B) at least one compound selected from:

-   -   (B-1) an organometallic compound,    -   (B-2) an organoaluminum oxy-compound and    -   (B-3) a compound capable of forming an ion pair by reacting with        the transition metal compound (A), and optionally

(C) a particle carrier.

Each component will be described in detail hereinbelow.

(B-1) Organometallic Compound

The organometallic compound (B-1) for use in the present invention is acompound of an organic metal compound selected from Group 1, 2, 12 and13, for example:

(B-1a) organoaluminum compounds represented by:R^(a) _(m)Al(OR^(b))_(n)H_(p)X_(q)wherein R^(a) and R^(b), which may be the same or different, are each ahydrocarbon group of 1 to 15, preferably 1 to 4 carbon atoms, X is ahalogen atom, 0<m≦3, 0≦n≦3, 0≦p<3, 0≦q<3 and m+n+p+q=3, such astrimethylaluminum, triethylaluminum, triisobutylaluminum anddiisobutylaluminumhydride;(B-1b) alkyl complex compounds of Group 1 metal and aluminum,represented by:M²AlR^(a) ₄wherein M² is Li, Na or K, and R^(a) is a hydrocarbon group of 1 to 15,preferably 1 to 4 carbon atoms, such as LiAl(C₂H₅)₄ and LiAl(C₇H₁₅)₄;(B-1c) dialkyl compounds of Group 2 or 12 metal, represented by:R^(a)R^(b)M³wherein R^(a) and R^(b), which may be the same or different, are each ahydrocarbon group of 1 to 15, preferably 1 to 4 carbon atoms, and M³ isMg, Zn or Cd.

Of the above organometallic compounds (B-1), the organoaluminumcompounds are preferred. The organometallic compounds (B-1) may be usedindividually or in combination of two or more kinds.

(B-2) Organoaluminum Oxy-Compound

The organoaluminum oxy-compound (B-2) for use in the present inventionmay be a conventional aluminoxane, or a benzene-insoluble organoaluminumoxy-compound as disclosed in JP-A-H02-78687.

For example, the conventional aluminoxanes may be prepared by thefollowing methods, and are normally obtained as solution in ahydrocarbon solvent.

(1) An organoaluminum compound, such as trialkylaluminum, is added to ahydrocarbon medium suspension of a compound containing absorbed water ora salt containing water of crystallization (such as magnesium chloridehydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickelsulfate hydrate or cerous chloride hydrate), to react the organoaluminumcompound with the absorbed water or water of crystallization.

(2) Water, ice or water vapor is allowed to react directly with anorganoaluminum compound, such as trialkylaluminum, in such a medium asbenzene, toluene, diethylether or tetrahydrofuran.

(3) An organoaluminum compound, such as trialkylaluminum, is reactedwith an organotin oxide, such as dimethyltin oxide or dibutyltin oxide,in such a medium as decane, benzene or toluene.

The aluminoxane may contain small amounts of organometallic components.After the solvent and unreacted organoaluminum compound are distilledaway from the recovered solution of the aluminoxane, the remainder maybe redissolved in a solvent or suspended in a poor solvent for thealuminoxane. Examples of the organoaluminum compound used in preparingthe aluminoxane include the compounds listed as the organoaluminumcompounds (B-1a). Of those compounds, trialkylaluminum andtricycloalkylaluminum are preferred, and trimethylaluminum isparticularly preferred. The organoaluminum compounds may be usedindividually or in combination of two or more kinds.

The benzene-insoluble organoaluminum oxy-compound of the presentinvention desirably contains Al components that will dissolve in 60° C.benzene, in an amount of 10% or less, preferably 5% or less, andparticularly preferably 2% or less in terms of Al atom. That is, theorganoaluminum oxy-compound is preferably insoluble or hardly soluble inbenzene. The organoaluminum oxy-compounds (B-2) may be used individuallyor in combination of two or more kinds.

(B-3) Compound Capable of Forming an Ion Pair by Reacting with theTransition Metal Compound

The compound (B-3) capable of forming an ion pair by reacting with thetransition metal compound (A) (hereinafter the “ionizing ioniccompound”) of the present invention can be selected from, for example,the Lewis acids, ionic compounds, borane compounds and carboranecompounds disclosed in JP-A-H01-501950, JP-A-H01-502036,JP-A-H03-179005, JP-A-H03-179006, JP-A-H03-207703, JP-A-H03-207704 andU.S. Pat. No. 5,321,106. Further, heteropoly compounds and isopolycompounds are also employable. These ionizing ionic compounds (B-3) maybe used individually or in combination of two or more kinds. When thetransition metal compound of the present invention is used incombination with the organoaluminum oxy-compound (B-2), for examplemethyl aluminoxane, as an auxiliary catalyst component, the resultantolefin polymerization catalyst will exhibit particularly highpolymerization activity for olefin compounds.

In addition to the transition metal compound (A) and at least onecompound (B) of the organometallic compound (B-1), the organoaluminumoxy-compound (B-2) and the ionizing ionic compound (B-3), the olefinpolymerization catalyst may optionally contain a carrier (C).

(C) Carrier

The carrier (C) used in the present invention is an inorganic or organicsolid compound of granular or fine particle state. Preferred inorganiccompounds include porous oxides, inorganic chlorides, clays, clayminerals and ion-exchange layered compounds.

Suitable porous oxides include SiO₂, Al₂O₃, MgO, ZrO₂, TiO₂, B₂O₃, CaO,ZnO, BaO, ThO₂, and composites and mixtures thereof such as natural orsynthetic zeolites, SiO₂—MgO, SiO₂—Al₂O₃, SiO₂—TiO₂, SiO₂—V₂O₅,SiO₂—Cr₂O₃ and SiO₂—TiO₂—MgO. Of these, porous oxides whose maincomponents are SiO₂ and/or Al₂O₃ are preferable. The porous oxides havevarious properties depending on the types and how they are produced. Thecarrier used in the present invention desirably ranges in particlediameter from 5 to 300 μm, preferably from 10 to 200 μm, and in specificsurface area from 50 to 1000 m²/g, preferably 100 to 700 m²/g, and inpore volume from 0.3 to 3.0 cm³/g. The carrier may optionally becalcined at 100 to 1000° C., preferably at 150 to 700° C. prior to use.

Suitable inorganic chlorides include MgCl₂, MgBr₂, MnCl₂ and MnBr₂. Theinorganic chlorides may be used directly or after ground by a ball millor a vibration mill. Alternative prior-to-use treatment is such that theinorganic chlorides are dissolved in a solvent, such as alcohol, and areseparated out as fine particles by means of a separating agent.

The clay for use in the present invention mainly comprises a claymineral. The ion-exchange layered compound for use in the presentinvention has a crystal structure in which planes formed by ionic bondspile parallel one another with weak bonding strength, and containsexchangeable ions. Most clay minerals are the ion-exchange layeredcompounds. The clays, clay minerals and ion-exchange layered compoundsmay be natural or synthetic. Examples of the clays, clay minerals andion-exchange layered compounds include clays, clay minerals and ioniccrystalline compounds having a layered crystal structure such ashexagonal closest packing structure, antimony structure, CdCl₂ structureor CdI₂ structure. Exemplary clays and clay minerals include kaolin,bentonite, kibushi clay, potter's clay, allophane, hisingerite,pyrophyllite, mica, montmorillonite, vermiculite, chlorite,palygorskite, kaolinite, nacrite, dickite and halloysite. Exemplaryion-exchange layered compounds include crystalline acid salts ofpolyvalent metals, such as α-Zr(HAsO₄)₂.H₂O, α-Zr(HPO₄)₂,α-Zr(KPO₄)₂.3H₂O, α-Ti(HPO₄)₂, α-Ti(HAsO₄)₂.H₂O, α-Sn(HPO₄)₂.H₂O,γ-Zr(HPO₄)₂, γ-Ti(HPO₄)₂ and γ-Ti(NH₄PO₄)₂.H₂O. Preferably, the claysand clay minerals of the present invention are chemically treated. Thechemical treatment may be, for example, a surface treatment to removeimpurities adhering to the surface or a treatment affecting the crystalstructure of the clay. Examples of such chemical treatments include acidtreatment, alkali treatment, salt treatment and organic substancetreatment.

The ion-exchange layered compound used in the present invention may beenlarged in interlaminar spacing by replacing the exchangeable ionsbetween layers with larger and bulkier ions by means of its ionexchangeability. The bulkier ions play a role as supporting columns inthe layered structure, and are generally called pillars. Introduction ofdifferent compounds between layers of a layered compound is calledintercalation. Guest compounds for the intercalation include cationicinorganic compounds such as TiCl₄ and ZrCl₄, metallic alkoxides such asTi(OR)₄, Zr(OR)₄, PO(OR)₃ and B(OR)₃ (wherein R is a hydrocarbon groupor the like), and metallic hydroxide ions such as [Al₁₃O₄(OH)₂₄]⁷⁺,[Zr₄(OH)₁₄]²⁺ and [Fe₃O(OCOCH₃)₆]⁺. These compounds may be usedindividually or in combination of two or more kinds. The intercalationof these compounds may be carried out in the presence of polymersobtained by hydrolysis of metallic alkoxides such as Si(OR)₄, Al(OR)₃and Ge(OR)₄ (wherein R is a hydrocarbon group or the like), or in thepresence of colloidal inorganic compounds such as SiO₂. Exemplarypillars include oxides which occur as a result of thermal dehydrationafter the metallic hydroxide ions have been intercalated between layers.Of the inorganic compounds, the clays and clay minerals, particularlymontmorillonite, vermiculite, pectolite, taeniolite and synthetic mica,are preferred.

Exemplary organic compounds include granular or particulate solidsranging from 5 to 300 μm in particle diameters. Specific examplesinclude (co)polymers mainly comprising α-olefins of 2 to 14 carbon atomssuch as ethylene, propylene, 1-butene and 4-methyl-1-pentene;(co)polymers mainly comprising vinylcyclohexane and styrene; andmodified products thereof.

In addition to the aforementioned transition metal compound (A), atleast one compound (B) of the organometallic compound (B-1), theorganoaluminum oxy-compound (B-2) and the ionizing ionic compound (B-3),and optional carrier (C), the olefin polymerization catalyst of thepresent invention may optionally contain a specific organic compoundcomponent (D).

(D) Organic Compound Component

The organic compound component (D) of the present invention is usedoptionally for the purpose of improving the polymerization activity andobtaining polymers with enhanced properties. Examples of the organiccompound include, although not limited thereto, alcohols, phenoliccompounds, carboxylic acids, phosphorous compounds and sulfonates.

In carrying out polymerization, the above components may be usedarbitrarily in any addition sequence. Some examples are given below:

(1) The component (A) alone is fed to a polymerization reactor.

(2) The components (A) and (B) are fed to a polymerization reactor inarbitrary sequence.

(3) A catalyst component in which the component (A) is supported on thecarrier (C), and the component (B) are fed to a polymerization reactorin arbitrary sequence.

(4) A catalyst component in which the component (B) is supported on thecarrier (C), and the component (A) are fed to a polymerization reactorin arbitrary sequence.

(5) A catalyst component in which the components (A) and (B) aresupported on the carrier (C) is fed to a polymerization reactor.

In the above methods (2) to (5), the two or more catalyst components maybe previously in contact with each other when they are fed to apolymerization reactor. In the method (4) and (5) in which the component(B) is supported on the carrier, an unsupported component (B) may beadded at an arbitrary sequence according to necessity. The supportedcomponent (B) and the unsupported component (B) may be the same ordifferent. The solid catalyst component in which the component (A) issupported on the component (C) or in which the components (A) and (B)are supported on the component (C), may be prepolymerized with anolefin. Another catalyst component may be supported on theprepolymerized solid catalyst component.

In the production process for olefin polymers according to the presentinvention, one or more olefins are polymerized or copolymerized in thepresence of the aforesaid olefin polymerization catalyst to give olefinpolymers. The polymerization may be carried out by a liquid-phasepolymerization process, such as solution polymerization or suspensionpolymerization, or a gas-phase polymerization process. The liquid-phasepolymerization may be conducted using an inert hydrocarbon solvent.Examples thereof include aliphatic hydrocarbons such as propane, butane,pentane, hexane, heptane, octane, decane, dodecane and kerosine;alicyclic hydrocarbons such as cyclopentane, cyclohexane andmethylcyclopentane; aromatic hydrocarbons such as benzene, toluene andxylene; halogenated hydrocarbons such as ethylene chloride,chlorobenzene and dichloromethane; and mixtures thereof. The olefinitself can work as a solvent.

In carrying out polymerization of olefins in the presence of the olefinpolymerization catalyst, the component (A) is used in an amount of 10⁻⁸to 10⁻² mol, preferably 10⁻⁷ to 10⁻³ mol per liter of the reactionvolume. The component (B-1) is used in an amount such that the molarratio ((B-1)/M) of the component (B-1) to all the transition metal atoms(M) in the component (A) will be 0.01 to 5000, preferably 0.05 to 2000.The component (B-2) is used in an amount such that the molar ratio((B-2)/M) of the component (B-2) in terms of aluminum atom to all thetransition metal atoms (M) in the component (A) will be 10 to 5000,preferably 20 to 2000. The component (B-3) is used in an amount suchthat the molar ratio ((B-3)/M) of the component (B-3) to the transitionmetal atoms (M) in the component (A) will be 1 to 10, preferably 1 to 5.

The component (D) is used in an amount such that:

the molar ratio ((D)/(B-1)) will be 0.01 to 10, preferably 0.1 to 5 inthe case that the component (B) is the component (B-1);

the molar ratio ((D)/(B-2)) will be 0.01 to 2, preferably 0.005 to 1 inthe case that the component (B) is the component (B-2); and

the molar ratio ((D)/(B-3)) will be 0.01 to 10, preferably 0.1 to 5 inthe case that the component (B) is the component (B-3).

The olefin polymerization using the olefin polymerization catalyst isgenerally conducted at −50 to +200° C., preferably 0 to 170° C. Thepolymerization pressure may range from atmospheric pressure to 10 MPa(gauge pressure), preferably from atmospheric pressure to 5 MPa (gaugepressure). The polymerization can be carried out batchwise,semi-continuously or continuously, and in two or more stages underdifferent conditions. The molecular weights of resulting olefin polymersmay be adjusted by adding hydrogen to the polymerization system, bycontrolling the polymerization temperature or by changing the amount ofthe component (B). When hydrogen is added, the addition is suitablyconducted at 0.001 to 100 NL based on 1 kg of olefin.

For the polymerization of the present invention, at least one monomer ispreferably selected from ethylene and α-olefins, in which ethylene orpropylene is an essential monomer. Examples of the α-olefins includelinear or branched α-olefins of 3 to 20, preferably 3 to 10 carbonatoms, such as propylene, 1-butene, 2-butene, 1-pentene,3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene,1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene,1-octadecene and 1-eicosene. Suitable monomers further includecycloolefins of 3 to 30, preferably 3 to 20 carbon atoms, such ascyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene,tetracyclododecene and2-methyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene; polarmonomers, such as α,β-unsaturated carboxylic acids, including acrylicacid, methacrylic acid, fumaric acid, maleic anhydride, itaconic acid,itaconic anhydride and bicyclo[2.2.1]-5-heptene-2,3-dicarboxylicanhydride, and metal salts thereof with sodium, potassium, lithium,zinc, magnesium and calcium; α,β-unsaturated carboxylates, such asmethyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate,n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, 2-ethylhexylacrylate, methyl methacrylate, ethyl methacrylate, n-propylmethacrylate, isopropyl methacrylate, n-butyl methacrylate and isobutylmethacrylate; vinyl esters, such as vinyl acetate, vinyl propionate,vinyl caproate, vinyl caprate, vinyl laurate, vinyl stearate and vinyltrifluoroacetate; and unsaturated glycidyls, such as glycidyl acrylate,glycidyl methacrylate and monoglycidyl itaconate. Also, thepolymerization can be carried out in the presence of vinylcyclohexanes,dienes, polyenes and aromatic vinyl compounds; for example, styrene andmono- or poly-alkyl styrenes, such as o-methylstyrene, m-methylstyrene,p-methylstyrene, o,p-dimethylstyrene, o-ethylstyrene, m-ethylstyrene andp-ethylstyrene; styrene derivatives containing a functional group, suchas methoxystyrene, ethoxystyrene, vinylbenzoic acid, vinylmethylbenzoate, vinylbenzyl acetate, hydroxystyrene, o-chlorostyrene,p-chlorostyrene and divinylbenzene; and 3-phenylpropylene,4-phenylpropylene and α-methylstyrene.

In the olefin polymerization as described above, at least one monomer isethylene or propylene. When two or more monomers are used, either theethylene or propylene, or both the ethylene and propylene willpreferably have an amount of 50 mol % or more relative to all themonomers. The process described above may be favorably used to produce,for example, ethylene/propylene copolymers (EPR), propylene/ethylenecopolymers (PER), propylene/ethylene random copolymers (random PP),propylene/ethylene block copolymers (block PP) and propylene/butenerandom copolymers (PBR).

Next, the polyolefin resin composition according to the presentinvention will be described in detail.

The polyolefin resin composition of the present invention comprises apropylene polymer (PP-C) and an elastomer (EL).

Each component for the polyolefin resin composition of the presentinvention will be described in detail hereinbelow.

Propylene Polymer (PP-C)

The propylene polymer (PP-C) for incorporating to the polyolefin resincomposition of the present invention may be a propylene homopolymer or arandom copolymer of propylene and ethylene, and/or an α-olefin having 4to 20 carbon atoms.

The α-olefins of 4 to 20 carbon atoms include 1-butene, 1-pentene,1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene,1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, norbornene,tetracyclododecene, butadiene, pentadiene, isoprene and hexadiene.

The propylene polymer (PP-C) desirably has a melting point (Tm) of 140°C. or above, preferably 145° C. or above, more preferably 150° C. orabove, and even more preferably 155° C. or above. Herein, the meltingpoint (Tm) is measured on a differential scanning calorimeter (DSC) inwhich a polymer sample is heated at 240° C. for 10 minutes, cooled to30° C. and maintained at the temperature for 5 minutes, and heated againat a rate of 10° C./min to obtain a peak attributed to the fusion of thecrystalline polymer. Lower melting points are unfavorable since theylead to poorer mechanical strength such as low rigidity.

The propylene polymer (PP-C) desirably has a melt flow rate (MFR), asmeasured at 230° C. and under a load of 2.16 kg in accordance with ASTMD1238, of 0.01 to 1000 g/min, preferably 0.05 to 500 g/min.

Although the propylene polymer (PP-C) may be selected from commerciallyavailable propylene polymers without limitation, it preferably has aratio (Mw/Mn) of 1 to 4, more preferably 1.1 to 3.5 in terms of aweight-average molecular weight (Mw) to a number-average molecularweight (Mn) measured by gel permeation chromatography (GPC). Excessivelybroad molecular weights bring about bad appearance of molded articles.

The propylene polymer (PP-C) may be prepared using a magnesium-supportedtitanium catalyst system or a metallocene catalyst system.

The magnesium-supported titanium catalyst system is desirably comprisedof a solid titanium catalyst component (I) essentially containingtitanium, magnesium and halogen, an organometallic compound catalystcomponent (II), and optionally an electron donor (III).

[Solid Titanium Catalyst Component (I)]

The solid titanium catalyst component (I) can be prepared by contactinga magnesium compound, a titanium compound and an electron donor asdescribed below.

(Magnesium Compound)

The magnesium compounds include those magnesium compounds with orwithout reducing ability.

Examples of the magnesium compounds with reducing ability includeorganomagnesium compounds represented by the following formula:X_(n)MgR_(2-n)wherein 0≦n<2; R denotes a hydrogen atom, an alkyl group of 1 to 20carbon atoms, an aryl group or a cycloalkyl group; when n is 0, two R'smay be the same or different; and X is a halogen.

Specific examples of the organomagnesium compounds with reducing abilityinclude alkylmagnesium compounds, such as dimethylmagnesium,diethylmagnesium, dipropylmagnesium, dibutylmagnesium, diamylmagnesium,dihexylmagnesium, didecylmagnesium, octylbutylmagnesium andethylbutylmagnesium; alkylmagnesium halides, such as ethylmagnesiumchloride, propylmagnesium chloride, butylmagnesium chloride,hexylmagnesium chloride and amylmagnesium chloride; alkylmagnesiumalkoxides, such as butylethoxymagnesium, ethylbutoxymagnesium andoctylbutoxymagnesium; butylmagnesium hydrides and magnesium hydrides.

Metallic magnesium is also employable.

Specific examples of the magnesium compounds without reducing abilityinclude halogenated magnesiums, such as magnesium chloride, magnesiumbromide, magnesium iodide and magnesium fluoride; alkoxymagnesiumhalides, such as methoxymagnesium chloride, ethoxymagnesium chloride,isopropoxymagnesium chloride, butoxymagnesium chloride andoctoxymagnesium chloride; aryloxymagnesium halides, such asphenoxymagnesium chloride and methylphenoxymagnesium chloride;dialkoxymagnesiums, such as diethoxymagnesium, diisopropoxymagnesium,dibutoxymagnesium, di-n-octoxymagnesium, di-2-ethylhexoxymagnesium andmethoxyethoxymagnesium; diaryloxymagnesiums, such as diphenoxymagnesium,di-methylphenoxymagnesium and phenoxymethylphenoxymagnesium; andmagnesium carboxylates, such as magnesium laurate and magnesiumstearate.

The magnesium compounds without reducing ability may be the compoundsderived from the magnesium compounds with reducing ability or may be thecompounds derived at the preparation of the catalyst component. Themagnesium compounds without reducing ability can be derived from themagnesium compounds with reducing ability by bringing the magnesiumcompounds with reducing ability into contact with, for example, apolysiloxane compound, a halogen-containing silane compound, ahalogen-containing aluminum compound, an ester-containing,alcohol-containing or halogen-containing compound or a compound havingan OH group or an active carbon-oxygen bond.

The magnesium compounds with and without reducing ability may each forma complex compound or a composite compound with other metal, such asaluminum, zinc, boron, beryllium, sodium or potassium, or may each be amixture with other metallic compound. The magnesium compounds may beused either individually or in combination of two or more kinds.

The solid magnesium compounds among the above-mentioned magnesiumcompounds may be liquefied by use of an electron donor (i). Examples ofthe electron donor (i) include alcohols, phenols, ketones, aldehydes,ethers, amines, pyridines and metallic acid esters.

Specific examples thereof include:

alcohols of 1 to 18 carbon atoms, such as methanol, ethanol, propanol,butanol, pentanol, hexanol, 2-ethylhexanol, octanol, dodecanol,octadecyl alcohol, oleyl alcohol, benzyl alcohol, phenylethyl alcohol,cumyl alcohol, isopropyl alcohol and isopropylbenzyl alcohol;

halogen-containing alcohols of 1 to 18 carbon atoms, such astrichloromethanol, trichloroethanol and trichlorohexanol;

alkoxyalcohols, such as 2-propoxyethanol, 2-butoxyethanol,2-ethoxypropanol, 3-ethoxypropanol, 1-methoxybutanol, 2-methoxybutanoland 2-ethoxybutanol;

phenols of 6 to 20 carbon atoms which may have a lower alkyl group, suchas phenol, cresol, xylenol, ethylphenol, propylphenol, nonylphenol,cumylphenol and naphthol;

ketones of 3 to 15 carbon atoms, such as acetone, methyl ethyl ketone,methyl isobutyl ketone, acetophenone, benzophenone and benzoquinone;

aldehydes of 2 to 15 carbon atoms, such as acetaldehyde,propionaldehyde, octyl aldehyde, benzaldehyde, tolualdehyde andnaphthaldehyde;

ethers of 2 to 20 carbon atoms, such as methyl ether, ethyl ether,isopropyl ether, butyl ether, amyl ether, tetrahydrofuran, anisole anddiphenyl ether;

amines, such as trimethylamine, triethylamine, tributylamine,tribenzylamine and tetramethylethylenediamine;

pyridines, such as pyridine, methylpyridine, ethylpyridine anddimethylpyridine; and

metallic acid esters, such as tetraethoxytitanium,tetra-n-propoxytitanium, tetra-i-propoxytitanium, tetrabutoxytitanium,tetrahexoxytitanium, tetrabutoxyzirconium and tetraethoxyzirconium.These may be used individually or in combination of two or more kinds.

Of the above compounds, the alcohols, the alkoxyalcohols and themetallic acid esters are particularly preferable.

Solubilization of the solid magnesium compound by use of the electrondonor (i) is normally conducted by contacting these two and optionallyheating the mixture. The contact temperature ranges from 0 to 200° C.,preferably from 20 to 180° C., and more preferably from 50 to 150° C.

The solubilization may be carried out in the presence of a hydrocarbonsolvent or the like. Exemplary hydrocarbon solvents include aliphatichydrocarbons, such as pentane, hexane, heptane, octane, decane,dodecane, tetradecane and kerosene; alicyclic hydrocarbons, such ascyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane,cyclooctane and cyclohexene; aromatic hydrocarbons, such as benzene,toluene and xylene; and halogenated hydrocarbons, such asdichloroethane, dichloropropane, trichloroethylene, chlorobenzene and2,4-dichlorotoluene.

There are many magnesium compounds other than those listed above thatcan be used in preparing the solid titanium catalyst component (I). Themagnesium compound preferably exists as a halogen-containing magnesiumcompound in the final solid titanium catalyst component (I); therefore,when the magnesium compound used contains no halogen, it is preferablybrought into contact with a halogen-containing compound in the course ofthe preparation.

In particular, the magnesium compounds without reducing ability arepreferred, and especially the halogen-containing magnesium compounds arepreferable. Of such compounds, magnesium chloride, alkoxymagnesiumchloride and aryloxymagnesium chloride are preferred.

(Titanium Compound)

The titanium compound used herein is preferably tetravalent. Exemplarytetravalent titanium compounds include those represented by the formula:Ti(OR)_(g)X_(4-g)wherein R is a hydrocarbon group, X is a halogen atom and 0≦g≦4.Specific examples of such compounds include tetrahalogenated titaniums,such as TiCl₄, TiBr₄ and TiI₄; trihalogenated alkoxytitaniums, such asTi(OCH₃)Cl₃, Ti(OC₂H₅)Cl₃, Ti(O n-C₄H₉)Cl₃, Ti(OC₂H₅)Br₃ andTi(O-iso-C₄H₉)Br₃; dihalogenated dialkoxytitaniums, such asTi(OCH₃)₂Cl₂, Ti(OC₂H₅)₂Cl₂, Ti(O n-C₄H₉)₂Cl₂ and Ti(OC₂H₅)₂Br₂;monohalogenated trialkoxytitaniums, such as Ti(OCH₃)₃Cl, Ti(OC₂H₅)₃Cl,Ti(O n-C₄H₉)₃Cl and Ti(OC₂H₅)₃Br; and tetraalkoxytitaniums, such asTi(OCH₃)₄, Ti(OC₂H₅)₄, Ti(O n-C₄H₉)₄, Ti(O iso-C₄H₉)₄ and Ti(O2-ethylhexyl)₄.

Of these, the tetrahalogenated titaniums are preferred, and titaniumtetrachloride is particularly preferred. The titanium compounds may beused individually or in combination of two or more kinds. The titaniumcompounds may be used together with an aromatic hydrocarbon, or may bediluted with a hydrocarbon or a halogenated hydrocarbon.

(Electron Donor (ii))

Preparation of the solid titanium catalyst component (I) preferablyinvolves the electron donor (ii). Exemplary electron donors (ii) includeacid halides, acid amides, nitriles, acid anhydrides, organic esters andpolyethers given below.

Specific examples include acid halides of 2 to 15 carbon atoms, such asacetyl chloride, benzoyl chloride, toluic chloride and anisic chloride;acid amides, such as N,N-dimethylacetamide, N,N-diethylbenzamide andN,N-dimethyltoluamide; nitriles, such as acetonitrile, benzonitrile andtolunitrile; acid anhydrides, such as acetic anhydride, phthalicanhydride and benzoic anhydride; and organic esters of 2 to 18 carbonatoms, such as methyl formate, methyl acetate, ethyl acetate, vinylacetate, propyl acetate, octyl acetate, cyclohexyl acetate, ethylpropionate, methyl butyrate, ethyl valerate, methyl chloroacetate, ethyldichloroacetate, methyl methacrylate, ethyl crotonate, ethylcyclohexanecarboxylate, methyl benzoate, ethyl benzoate, propylbenzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenylbenzoate, benzyl benzoate, methyl toluate, ethyl toluate, amyl toluate,ethyl ethylbenzoate, methyl anisate, ethyl anisate, ethylethoxybenzoate, γ-butyrolactone, δ-valerolactone, coumarin, phthalideand ethyl carbonate.

Examples of the organic esters further include polyvalent carboxylicacid esters having a skeleton represented by any of the followingformulae (1):

wherein R¹ denotes a substituted or unsubstituted hydrocarbon group; R²,R⁵ and R⁶ each denote hydrogen or a substituted or unsubstitutedhydrocarbon group; R³ and R⁴ each denote hydrogen or a substituted orunsubstituted hydrocarbon group, and at least one of the two ispreferably a substituted or unsubstituted hydrocarbon group; R³ and R⁴may link together to form a cyclic structure; and when the hydrocarbongroups R¹ to R⁶ are substituted, the substituent groups contain a heteroatom, such as N, O or S, to form a group as C—O—C, COOR, COOH, OH, SO₃H,—C—N—C— or NH₂.

Specific examples of the polyvalent carboxylic acid esters includealiphatic polycarboxylates, alicyclic polycarboxylates, aromaticpolycarboxylates and heterocyclic polycarboxylates.

Preferred examples of the polyvalent carboxylic acid esters with theskeletons represented by the formulae (1) include diethyl succinate,dibutyl succinate, diethyl methylsuccinate, diaryl methylsuccinate,diisobutyl α-methylglutarate, diisopropyl β-methylglutarate, diisobutylmethylmalonate, dibutyl ethylmalonate, diethyl ethylmalonate, diethylisopropylmalonate, dibutyl isopropylmalonate, dibutyl butylmalonate,dibutyl phenylmalonate, diethyl diethylmalonate, dibutyldibutylmalonate, diethyl dibutylmalonate, n-butyl maleate, dibutylmethylmaleate, dibutyl butylmaleate, di-2-ethylhexyl fumarate,di-n-hexyl cyclohexenecarboxylate, diethyl nadiate, diisopropyltetrahydrophthalate, diethyl phthalate, monoethyl phthalate, dipropylphthalate, diisobutyl phthalate, diisopropyl phthalate, ethylisobutylphthalate, di-n-butyl phthalate, di-n-heptyl phthalate, di-n-octylphthalate, di-2-ethylhexyl phthalate, di(2-methylpentyl)phthalate,di(3-methylpentyl)phthalate, di(4-methylpentyl)phthalate,di(2,3-dimethylbutyl)phthalate, di(3-methylhexyl)phthalate,di(4-methylhexyl)phthalate, di(5-methylhexyl)phthalate,di(3-ethylpentyl)phthalate, di(3,4-dimethylpentyl)phthalate,di(2,4-dimethylpentyl)phthalate, di(2-methylhexyl)phthalate,di(2-methyloctyl)phthalate, didecyl phthalate, diphenyl phthalate andmixtures of these phthalic acid diesters, diethylnaphthalenedicarboxylate, dibutyl naphthalenedicarboxylate, triethyltrimellitate, tributyl trimellitate, dibutyl 3,4-furandicarboxylate,diethyl adipate, dibutyl adipate, dioctyl sebacate and dibutyl sebacate.

Of these, the phthalic acid diesters are preferably used.

Exemplary electron donors further include compounds in which at leasttwo ether bonds are present via plural atoms (such compounds will bereferred to also as “polyethers” hereinafter). Examples of thepolyethers include compounds in which the atoms between the ether bondsare carbon, silicon, oxygen, nitrogen, phosphorus, boron, sulfur or atleast two of them. Of such compounds, preferable are the compounds inwhich a relatively bulky substituent group is bonded to the atom betweenthe ether bonds and further in which the atoms between the 2 or moreether bonds include plural carbon atoms. For example, the polyethersrepresented by the following formula (2) are preferable:

wherein n is an integer of 2≦n≦10, R¹ to R²⁶ each denote a substituentgroup having at least one element selected from carbon, hydrogen,oxygen, halogen, nitrogen, sulfur, phosphorus, boron and silicon;arbitrary groups of R¹ to R²⁶, preferably of R¹ to R^(2n) may form inassociation a ring other than the benzene ring; and the main chain maycontain atoms other than carbon.

Specific examples of the polyether compounds include2-(2-ethylhexyl)-1,3-dimethoxypropane, 2-isopropyl-1,3-dimethoxypropane,2-butyl-1,3-dimethoxypropane, 2-s-butyl-1,3-dimethoxypropane,2-cyclohexyl-1,3-dimethoxypropane, 2-phenyl-1,3-dimethoxypropane,2-cumyl-1,3-dimethoxypropane, 2-(2-phenylethyl)-1,3-dimethoxypropane,2-(2-cyclohexylethyl)-1,3-dimethoxypropane,2-(p-chlorophenyl)-1,3-dimethoxypropane,2-(diphenylmethyl)-1,3-dimethoxypropane,2-(1-naphthyl)-1,3-dimethoxypropane,2-(2-fluorophenyl)-1,3-dimethoxypropane,2-(1-decahydronaphthyl)-1,3-dimethoxypropane,2-(p-t-butylphenyl)-1,3-dimethoxypropane,2,2-dicyclohexyl-1,3-dimethoxypropane, 2,2-diethyl-1,3-dimethoxypropane,2,2-dipropyl-1,3-dimethoxypropane, 2,2-dibutyl-1,3-dimethoxypropane,2-methyl-2-propyl-1,3-dimethoxypropane,2-methyl-2-benzyl-1,3-dimethoxypropane,2-methyl-2-ethyl-1,3-dimethoxypropane,2-methyl-2-isopropyl-1,3-dimethoxypropane,2-methyl-2-phenyl-1,3-dimethoxypropane,2-methyl-2-cyclohexyl-1,3-dimethoxypropane,2,2-bis(p-chlorophenyl)-1,3-dimethoxypropane,2,2-bis(2-cyclohexylethyl)-1,3-dimethoxypropane,2-methyl-2-isobutyl-1,3-dimethoxypropane,2-methyl-2-(2-ethylhexyl)-1,3-dimethoxypropane,2,2-diisobutyl-1,3-dimethoxypropane, 2,2-diphenyl-1,3-dimethoxypropane,2,2-dibenzyl-1,3-dimethoxypropane,2,2-bis(cyclohexylmethyl)-1,3-dimethoxypropane,2,2-diisobutyl-1,3-diethoxypropane, 2,2-diisobutyl-1,3-dibutoxypropane,2-isobutyl-2-isopropyl-1,3-dimethoxypropane,2,2-di-s-butyl-1,3-dimethoxypropane,2,2-di-t-butyl-1,3-dimethoxypropane,2,2-dineopentyl-1,3-dimethoxypropane,2-isopropyl-2-isopentyl-1,3-dimethoxypropane,2-phenyl-2-benzyl-1,3-dimethoxypropane,2-cyclohexyl-2-cyclohexylmethyl-1,3-dimethoxypropane,2,3-diphenyl-1,4-diethoxybutane, 2,3-dicyclohexyl-1,4-diethoxybutane,2,2-dibenzyl-1,4-diethoxybutane, 2,3-dicyclohexyl-1,4-diethoxybutane,2,3-diisopropyl-1,4-diethoxybutane,2,2-bis(p-methylphenyl)-1,4-dimethoxybutane,2,3-bis(p-chlorophenyl)-1,4-dimethoxybutane,2,3-bis(p-fluorophenyl)-1,4-dimethoxybutane,2,4-diphenyl-1,5-dimethoxypentane, 2,5-diphenyl-1,5-dimethoxyhexane,2,4-diisopropyl-1,5-dimethoxypentane,2,4-diisobutyl-1,5-dimethoxypentane, 2,4-diisoamyl-1,5-dimethoxypentane,3-methoxymethyltetrahydrofuran, 3-methoxymethyldioxane,1,2-diisobutoxypropane, 1,2-diisobutoxyethane, 1,3-diisoamyloxyethane,1,3-diisoamyloxypropane, 1,3-diisoneopentyloxyethane,1,3-dineopentyloxypropane, 2,2-tetramethylene-1,3-dimethoxypropane,2,2-pentamethylene-1,3-dimethoxypropane,2,2-hexamethylene-1,3-dimethoxypropane,1,2-bis(methoxymethyl)cyclohexane, 2,8-dioxaspiro[5,5]undecane,3,7-dioxabicyclo[3,3,1]nonane, 3,7-dioxabicyclo[3,3,0]octane,3,3-diisobutyl-1,5-oxononane, 6,6-diisobutyldioxyheptane,1,1-dimethoxymethylcyclopentane, 1,1-bis(dimethoxymethyl)cyclohexane,1-bis(methoxymethyl)bicyclo[2,2,1]heptane,1,1-dimethoxymethylcyclopentane,2-methyl-2-methoxymethyl-1,3-dimethoxypropane,2-cyclohexyl-2-ethoxymethyl-1,3-diethoxypropane,2-cyclohexyl-2-methoxymethyl-1,3-dimethoxypropane,2,2-diisobutyl-1,3-dimethoxycyclohexane,2-isopropyl-2-isoamyl-1,3-dimethoxycyclohexane,2-cyclohexyl-2-methoxymethyl-1,3-dimethoxycyclohexane,2-isopropyl-2-methoxymethyl-1,3-dimethoxycyclohexane,2-isobutyl-2-methoxymethyl-1,3-dimethoxycyclohexane,2-cyclohexyl-2-ethoxymethyl-1,3-diethoxycyclohexane,2-cyclohexyl-2-ethoxymethyl-1,3-dimethoxycyclohexane,2-isopropyl-2-ethoxymethyl-1,3-diethoxycyclohexane,2-isopropyl-2-ethoxymethyl-1,3-dimethoxycyclohexane,2-isobutyl-2-ethoxymethyl-1,3-diethoxycyclohexane and2-isobutyl-2-ethoxymethyl-1,3-dimethoxycyclohexane.

Exemplary polyethers further include tris(p-methoxyphenyl)phosphine,methylphenyl bis(methoxymethyl)silane, diphenylbis(methoxymethyl)silane, methylcyclohexyl bis(methoxymethyl)silane,di-t-butyl bis(methoxymethyl)silane, cyclohexyl-t-butylbis(methoxymethyl)silane and i-propyl-t-butyl bis(methoxymethyl)silane.

Of the polyether compounds, 2,2-diisobutyl-1,3-dimethoxypropane,2-isopropyl-2-isobutyl-1,3-dimethoxypropane,2-isopropyl-2-isopentyl-1,3-dimethoxypropane,2,2-dicyclohexyl-1,3-dimethoxypropane and2,2-bis(cyclohexylmethyl)-1,3-dimethoxypropane are preferred.

Of the electron donors (ii) described above, the organic esters and thepolyethers are preferable, and the aromatic diesters such as thephthalic acid diesters, and the polyethers are more preferably employed.The electron donors may be used individually or in combination of two ormore kinds. Further, compounds that can form the electron donors duringthe preparation of the solid titanium catalyst component (I) may be usedeven if they are not exactly the compounds as described above, since theabove-listed electron donors should be contained as such in the finalsolid titanium catalyst component (I). In this case too, such compoundsmay be used to form two or more kinds of the electron donors (ii).

(Preparation of the Solid Titanium Catalyst Component (I))

Various processes are available to prepare the solid titanium catalystcomponent (I) from the above compounds without limitation. Exemplarypreparation is presented below, in which the organometallic compoundused may be as detailed later as the organometallic compound (II).

(1) A solution essentially consisting of the magnesium compound, theelectron donor (i) and the hydrocarbon solvent is optionally broughtinto contact with an organometallic compound to cause precipitation of asolid. During or after the precipitation, the liquid titanium compoundis added to the reaction solution to form a solid component. The solidcomponent is reacted with the aromatic hydrocarbon, the liquid titaniumcompound and the electron donor (ii) by being brought into contacttherewith at least once, preferably several times.

(2) A product from the contact between the liquid organomagnesiumcompound and an inorganic or organic carrier is optionally brought intocontact with an organometallic compound to cause precipitation of asolid. During or after the precipitation, the liquid titanium compoundis added to the reaction solution to form a solid component. The solidcomponent is then reacted with the aromatic hydrocarbon, the liquidtitanium compound and the electron donor (ii) by being brought intocontact therewith at least once, preferably several times. Beforereaction with the aromatic hydrocarbon, etc., the solid component may bebrought into contact with a halogen-containing compound and/or anorganometallic compound.

[Organometallic Compound Catalyst Component (II)]

The organometallic compound catalyst component (II) preferably containsa metal selected from Group 13 of the periodic table. Particularly,organoaluminum compounds, organoboron compounds and alkyl complexcompounds of a Group 1 element and aluminum or boron are preferable. Forexample, the organoaluminum compounds may be represented by thefollowing formula:R^(a) _(n)AlX_(3-n)wherein R^(a) denotes a hydrocarbon group of 1 to 12 carbon atoms, Xdenotes a halogen or hydrogen, and n ranges from 1 to 3.

The hydrocarbon groups of 1 to 12 carbon atoms designated by R^(a)include alkyl, cycloalkyl and aryl groups. Specific examples thereofinclude methyl, ethyl, n-propyl, isopropyl, isobutyl, pentyl, hexyl,octyl, cyclopentyl, cyclohexyl, phenyl and tolyl groups.

Examples of such organoaluminum compounds include trialkylaluminums,such as trimethylaluminum, triethylaluminum, triisopropylaluminum,triisobutylaluminum, trioctylaluminum and tri-2-ethylhexylaluminum;trialkenylaluminums, such as triisoprenylaluminum; dialkylaluminumhalides, such as dimethylaluminum chloride, diethylaluminum chloride,diisopropylaluminum chloride, diisobutylaluminum chloride anddimethylaluminum bromide; alkylaluminum sesquihalides, such asmethylaluminum sesquichloride, ethylaluminum sesquichloride,isopropylaluminum sesquichloride, butylaluminum sesquichloride andethylaluminum sesquibromide; alkylaluminum dihalides, such asmethylaluminum dichloride, ethylaluminum dichloride, isopropylaluminumdichloride and ethylaluminum dibromide; and alkylaluminum hydrides, suchas diethylaluminum hydride, diisobutylaluminum hydride and ethylaluminumdihydride.

Compounds having the following formula may also be employed as theorganoaluminum compounds:R^(a) _(n)AlY_(3-n)wherein R^(a) is the same as described above; Y is a group representedby —OR^(b), —OSiR^(c) ₃, —OAlR^(d) ₂, —NR^(e) ₂, —SiR^(f) ₃ or—N(R^(g))AlR^(h) ₂; n is 1 or 2; R^(b), R^(c), R^(d) and R^(h) are eacha methyl, ethyl, isopropyl, isobutyl, cyclohexyl or phenyl group etc.;R^(e) is a hydrogen atom or a methyl, ethyl, isopropyl, phenyl ortrimethylsilyl group etc.; and R^(f) and R^(g) are each a methyl orethyl group etc.

Examples of such organoaluminum compounds include:

(I) Compounds represented by R^(a) _(n)Al(OR^(b))_(3-n), such asdimethylaluminum methoxide, diethylaluminum ethoxide anddiisobutylaluminum methoxide.

(II) Compounds represented by R^(a) _(n)Al(OSiR^(c))_(3-n), such asEt₂Al(OSiMe₃), (iso-Bu)₂Al(OSiMe₃) and (iso-Bu)₂Al(OSiEt₃).

(III) Compounds represented by R^(a) _(n)Al(OAlR^(d) ₂)_(3-n), such asEt₂AlOAlEt₂ and (iso-Bu)₂AlOAl(iso-Bu)₂.

(IV) Compounds represented by R^(a) _(n)Al(NR^(e) ₂)_(3-n), such asMe₂AlNEt₂, Et₂AlNHMe, Me₂AlNHEt, Et₂AlN(Me₃Si)₂ and(iso-Bu)₂AlN(Me₃Si)₂.

(V) Compounds represented by R^(a) _(n)Al(SiR^(f) ₃)_(3-n), such as(iso-Bu)₂AlSiMe₃.

(VI) Compounds represented by R^(a) _(n)Al[N(R^(g))—AlR^(h) ₂]_(3-n),such as Et₂AlN(Me)—AlEt₂ and (iso-Bu)₂AlN(Et)Al(iso-Bu)₂.

Further, compounds analogous to the above compounds, such asorganoaluminum compounds in which at least two aluminums are bonded viaan oxygen atom or a nitrogen atom, are also employable. Specificexamples thereof include (C₂H₅)₂AlOAl(C₂H₅)₂, (C₄H₉)₂AlOAl(C₄H₉)₂ and(C₂H₅)₂AlN(C₂H₅)Al(C₂H₅)₂. Furthermore, aluminoxanes (organoaluminumoxy-compounds), such as methyl aluminoxane, may also be used.

Organoaluminum compounds represented by the following formula are alsoemployable:R^(a)AlXYwherein R^(a), X and Y are the same as mentioned above.

Examples of the organoboron compounds include triphenylboron,tris(4-fluorophenyl)boron, tris(3,5-difluorophenyl)boron,tris(4-fluoromethylphenyl)boron, tris(pentafluorophenyl)boron,tris(p-tolyl)boron, tris(o-tolyl)boron, tris(3,5-dimethylphenyl)boron,thexylborane, dicyclohexylborane, dicyamylborane,diisopinocamphenylborane, 9-borabicyclo[3.3.1]nonane, catecholborane,B-bromo-9-borabicyclo[3.3.1]nonane, borane-triethylamine complex andborane-methylsulfide complex.

Ionic compounds may be used as the organoboron compounds. Examples ofsuch compounds include triethylammonium tetra(phenyl)boron,tripropylammonium tetra(phenyl)boron, trimethylammoniumtetra(p-tolyl)boron, trimethylammonium tetra(o-tolyl)boron,tri(n-butyl)ammonium tetra(pentafluorophenyl)boron, tripropylammoniumtetra(o,p-dimethylphenyl)boron, tri(n-butyl)ammoniumtetra(p-trifluoromethylphenyl)boron, N,N-dimethylaniliniumtetra(phenyl)boron, dicyclohexylammonium tetra(phenyl)boron,triphenylcarbenium tetrakis(pentafluorophenyl)borate,N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate,bis[tri(n-butyl)ammonium]nonaborate andbis[tri(n-butyl)ammonium]decaborate.

The alkyl complex compounds of a Group 1 element and aluminum includecompounds represented by the following formula:M¹AlR^(j) ₄wherein M¹ denotes Li, Na or K, and R^(j) denotes a hydrocarbon group of1 to 15 carbon atoms.

Specific examples thereof include LiAl(C₂H₅)₄ and LiAl(C₇H₁₅)₄.

Examples of the organoboron compounds and of the alkyl complex compoundsof a Group 1 element and boron include corresponding compounds to theorganoaluminum compounds and to the alkyl complex compounds of a Group 1element and aluminum except that the aluminum is substituted with boron,respectively.

[Electron Donor (III)]

Examples of the electron donor (III) include the compounds listed aboveas the electron donors (ii) for use in the preparation of the solidtitanium catalyst component (I), and further include organosiliconcompounds having the following formula:R_(n)Si(OR′)_(4-n)wherein R and R′ are each a hydrocarbon group and 0<n<4.

Specific examples of the organosilicon compounds represented by theabove formula include trimethylmethoxysilane, trimethylethoxysilane,dimethyldimethoxysilane, dimethyldiethoxysilane,diisopropyldimethoxysilane, tert-butylmethyldimethoxysilane,tert-butylmethyldiethoxysilane, tert-amylmethyldiethoxysilane,diphenyldimethoxysilane, phenylmethyldimethoxysilane,diphenyldiethoxysilane, bis-o-tolyldimethoxysilane,bis-m-tolyldimethoxysilane, bis-p-tolyldimethoxysilane,bis-p-tolyldiethoxysilane, bis-ethylphenyldimethoxysilane,dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane,cyclohexylmethyldiethoxysilane, ethyltrimethoxysilane,ethyltriethoxysilane, vinyltrimethoxysilane, methyltrimethoxysilane,n-propyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane,phenyltrimethoxysilane, γ-chloropropyltrimethoxysilane,methyltriethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane,tert-butyltriethoxysilane, n-butyltriethoxysilane,iso-butyltriethoxysilane, phenyltriethoxysilane,γ-aminopropyltriethoxysilane, chlorotriethoxysilane,ethyltriisopropoxysilane, vinyltributoxysilane,cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane,2-norbornanetrimethoxysilane, 2-norbornanetriethoxysilane,2-norbornanemethyldimethoxysilane, ethyl silicate, butyl silicate,trimethylphenoxysilane, methyltriallyloxysilane, vinyltris(β-methoxyethoxysilane), vinyltriacetoxysilane,dimethyltetraethoxydisiloxane, cyclopentyltrimethoxysilane,2-methylcyclopentyltrimethoxysilane,2,3-dimethylcyclopentyltrimethoxysilane, cyclopentyltriethoxysilane,dicyclopentyldimethoxysilane, bis(2-methylcyclopentyl)dimethoxysilane,bis(2,3-dimethylcyclopentyl)dimethoxysilane,dicyclopentyldiethoxysilane, tricyclopentylmethoxysilane,tricyclopentylethoxysilane, dicyclopentylmethylmethoxysilane,dicyclopentylethylmethoxysilane, hexenyltrimethoxysilane,dicyclopentylmethylethoxysilane, cyclopentyldimethylmethoxysilane,cyclopentyldiethylmethoxysilane and cyclopentyldimethylethoxysilane.

Of these, preferable are ethyltriethoxysilane, n-propyltriethoxysilane,tert-butyltriethoxysilane, vinyltriethoxysilane, phenyltriethoxysilane,vinyltributoxysilane, diphenyldimethoxysilane,phenylmethyldimethoxysilane, bis-p-tolyldimethoxysilane,p-tolylmethyldimethoxysilane, dicyclohexyldimethoxysilane,cyclohexylmethyldimethoxysilane, 2-norbornanetriethoxysilane,2-norbornanemethyldimethoxysilane, phenyltriethoxysilane,dicyclopentyldimethoxysilane, hexenyltrimethoxysilane,cyclopentyltriethoxysilane, tricyclopentylmethoxysilane andcyclopentyldimethylmethoxysilane.

Further examples of the electron donor (III) include nitrogen-containingelectron donors, such as 2,6-substituted piperidines, 2,5-substitutedpiperidines, substituted methylenediamines (e.g.N,N,N′,N′-tetramethylmethylenediamine andN,N,N′,N′-tetraethylmethylenediamine), and substituted imidazolidines(e.g. 1,3-dibenzylimidazolidine and 1,3-dibenzyl-2-phenylimidazolidine);phosphorus-containing electron donors, such as phosphites, includingtriethyl phosphite, tri-n-propyl phosphite, triisopropyl phosphite,tri-n-butyl phosphite, triisobutyl phosphite, diethyl-n-butyl phosphiteand diethylphenyl phosphite; and oxygen-containing electron donors, suchas 2,6-substituted tetrahydropyrans and 2,5-substitutedtetrahydropyrans. The electron donors (III) may be used individually orin combination of two or more kinds.

The metallocene catalyst comprises a metallocene compound (a), at leastone compound selected from an organometallic compound (b-1), anorganoaluminum oxy-compound (b-2) and a compound (b-3) capable offorming an ion pair by reacting with the metallocene compound (a), andoptionally a fine particle carrier (c). Herein, the organometalliccompound (b-1), organoaluminum oxy-compound (b-2), compound (b-3)capable of forming an ion pair by reacting with the metallocene compound(a), and fine particle carrier (c) are used to refer to theorganometallic compound (B-1), organoaluminum oxy-compound (B-2),compound (B-3) capable of forming an ion pair by reacting with thetransition metal compound, and carrier (C), respectively.

The metallocene compound (a) is not particularly limited as far as thepropylene polymer (PP-C) that has the aforesaid properties results. Thetransition metal compound (1a) is a preferred example of the metallocenecompound, and particularly the transition metal compound (1a) of theformula (1a) in which R¹ is a hydrocarbon group or a silicon-containinggroup is preferable.

In carrying out polymerization, the catalyst components may be usedarbitrarily and in any addition sequence. Some exemplary processes aregiven below.

(1) The component (a) and at least one compound (b) selected from theorganometallic compound (b-1), the organoaluminum oxy-compound (b-2) andthe ionizing ionic compound (b-3) (hereinafter simply “component (b)”)are fed to a polymerization reactor in an arbitrary order.

(2) A catalyst resulting from the contact between the component (a) andthe component (b) is fed to a polymerization reactor.

(3) A catalyst component resulting from the contact between thecomponent (a) and the component (b), and the component (b) are fed to apolymerization reactor in an arbitrary order. In this case, thecomponents (b) may be the same or different.

(4) A catalyst component in which the component (a) is supported on thefine particle carrier (c), and the component (b) are fed to apolymerization reactor in an arbitrary order.

(5) A catalyst in which the components (a) and (b) are supported on thefine particle carrier (c) is fed to a polymerization reactor.

(6) A catalyst component in which the components (a) and (b) aresupported on the fine particle carrier (c), and the component (b) arefed to a polymerization reactor in an arbitrary order. In this case, thecomponents (b) may be the same or different.

(7) A catalyst component in which the component (b) is supported on thefine particle carrier (c), and the component (a) are fed to apolymerization reactor in an arbitrary order.

(8) A catalyst component in which the component (b) is supported on thefine particle carrier (c), the component (a) and the component (b) arefed to a polymerization reactor in an arbitrary order. In this case, thecomponents (b) may be the same or different.

(9) The components (a) and (b) are supported on the fine particlecarrier (c) to form a catalyst component, and the catalyst component isthen contacted with the component (b) to yield a catalyst, which is fedto a polymerization reactor. In this case, the components (b) may be thesame or different.

(10) The components (a) and (b) are supported on the fine particlecarrier (c), and are contacted with the component (b) to form a catalystcomponent. The catalyst component and the component (b) are fed to apolymerization reactor. In this case, the components (b) may be the sameor different.

The solid catalyst component in which the components (a) and (b) aresupported on the fine particle carrier (c), may be prepolymerized withan olefin. The prepolymerized solid catalyst component generallycontains the polyolefin in an amount of 0.1 to 1000 g, preferably 0.3 to500 g, and particularly preferably 1 to 200 g, based on 1 g of the solidcatalyst component.

To allow the polymerization to proceed smoothly, an antistatic agent, anantifouling agent and the like may be used, optionally in a supportedform on a carrier.

In the present invention, preparation of the propylene polymer (PP-C)may be carried out by any of liquid-phase polymerization, such assolution polymerization or suspension polymerization, and gas-phasepolymerization. The liquid-phase polymerization may be conducted usingan inert hydrocarbon solvent. Exemplary inert hydrocarbon solventsinclude aliphatic hydrocarbons, such as propane, butane, pentane,hexane, heptane, octane, decane, dodecane and kerosene; alicyclichydrocarbons, such as cyclopentane, cyclohexane and methylcyclopentane;aromatic hydrocarbons, such as benzene, toluene and xylene; halogenatedhydrocarbons, such as ethylene chloride, chlorobenzene anddichloromethane; and mixtures thereof. The α-olefin to be polymerizedmay work as a solvent itself.

The temperature in the olefin polymerization is usually in the range of−50 to 200° C., preferably 0 to 170° C. The polymerization pressuregenerally ranges from atmospheric pressure to 10 MPa (gauge pressure),preferably from atmospheric pressure to 5 MPa (gauge pressure). Thepolymerization reaction can be carried out batchwise, semi-continuouslyor continuously. Also, it is possible to conduct the polymerization intwo or more stages under different reaction conditions. Continuouspolymerization is preferable in the present invention.

Hydrogen may be used in the polymerization to control the molecularweights of polymers or the polymerization activity, and its amount maybe suitably in the range of about 0.001 to 100 NL based on 1 kg of theolefin.

The propylene polymer (PP-C) of the present invention may be preparedusing a magnesium-supported titanium catalyst system, a metallocenecatalyst system or the both. When the two catalyst systems are used incombination, polymerization is catalyzed by the magnesium-supportedtitanium catalyst system to give a polymer (A1) and by the metallocenecatalyst system to give a polymer (A2) in a weight ratio of 1/99 to99/1. The propylene polymer (A1) obtained with the magnesium-supportedtitanium catalyst system and the propylene polymer (A2) obtained withthe metallocene catalyst system may be mixed in a desirable weight ratioof 1/99 to 99/1, and preferably 5/95 to 95/5.

The metallocene-catalyzed propylene polymer (A2) has a ratio of 0.2% orless, respectively in terms of irregularly bonded propylene monomersbased on 2,1-insertion or 1,3-insertion to all the propylene structuralunits as determined from a ¹³C-NMR spectrum. When the ratio ofirregularly bonded propylene monomers based on 2,1-insertion or1,3-insertion increases, mechanical strength properties of the resultantresin composition are deteriorated.

Elastomer (EL)

The elastomers (EL) of the present invention for the polyolefin resincomposition include:

(EL-1) a random copolymer of propylene and ethylene that containspropylene-derived constituent units and ethylene-derived constituentunits in a molar ratio of 80/20 to 20/80;

(EL-2) a random copolymer of ethylene and an α-olefin having 4 to 20carbon atoms that contains ethylene-derived constituent units andα-olefin-derived constituent units in a molar ratio of 80/20 to 20/80;

(EL-3) a random copolymer of propylene and an α-olefin having 4 to 20carbon atoms that contains propylene-derived constituent units andα-olefin-derived constituent units in a molar ratio of 80/20 to 20/80;and

(EL-4) a random copolymer of ethylene, propylene and an α-olefin having4 to 20 carbon atoms that contains propylene-derived constituent unitsand α-olefin-derived constituent units in a molar ratio of 80/20 to20/80, and contains ethylene-derived and propylene-derived constituentunits (EP), and C₄₋₂₀ α-olefin-derived constituent units (OL) in a molarratio [(EP)/(OL)] of 99/1 to 20/80.

Exemplary α-olefins of 4 to 20 carbon atoms for the preparation of theelastomers (EL) include olefin compounds having 2 to 20 carbon atoms,such as 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene,1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene,1-eicosene, norbornene, tetracyclododecene, butadiene, pentadiene,isoprene and hexadiene.

Other employable compounds include linear polyene compounds such asmethylhexadiene, octadiene, methyloctadiene, ethyloctadiene,propyloctadiene, butyloctadiene, nonadiene, methylnonadiene,ethylnonadiene, decadiene, methyldecadiene, undecadiene,methylundecadiene, octatriene, decatriene and divinylbenzene; and cyclicpolyene compounds such as cyclopentadiene, cyclohexadiene,ethylcyclohexadiene, cycloheptadiene, dicyclopentadiene,dicyclohexadiene, ethylidenenorbornene, vinylnorbornene,isopropylidenenorbornene, methylhydroindene, diisopropylidenenorborneneand propenylisonorbornadiene.

These olefin compounds may be used singly or in combination of two ormore kinds. Of the above compounds, 1-butene, 1-hexene and 1-octene areparticularly preferable.

The elastomer (EL) has an intrinsic viscosity [η], as measured indecalin at 135° C., of 1.5 dl/g or more, preferably 2.0 dl/g or more,and more preferably 2.5 dl/g or above.

The elastomer (EL) desirably has a ratio (Mw/Mn) of 1.0 to 3.5,preferably 1.1 to 3.0 in terms of a weight-average molecular weight (Mw)to a number-average molecular weight (Mn) as measured by gel permeationchromatography (GPC).

The density of the elastomer (EL) desirably falls in the range of 0.85to 0.92 g/cm³, preferably 0.85 to 0.90 g/cm³.

Importantly, the elastomer (EL-1) for the polyolefin resin compositionof the present invention has a ratio of 1.0 mol % or less, preferably0.5 mol % or less, and more preferably 0.2 mol % or less in terms ofirregularly bonded propylene monomers based on 2,1-insertion to all thepropylene constituent units as determined from a ¹³C-NMR spectrum.

Also, it is important with respect to the polyolefin resin compositionof the present invention that the elastomer (EL-2) has a ratio of 1.0mol % or less, preferably 0.5 mol % or less, and more preferably 0.2 mol% or less in terms of irregularly bonded α-olefin monomers based on2,1-insertion to all the α-olefin constituent units as determined from a¹³C-NMR spectrum.

Further, the elastomer (EL-3) of the present invention for thepolyolefin resin composition should have a ratio of 1.0 mol % or less,preferably 0.5 mol % or less, and more preferably 0.2 mol % or less interms of irregularly bonded propylene monomers based on 2,1-insertion toall the propylene constituent units as determined from a ¹³C-NMRspectrum.

The elastomer (EL-3) has a melting point (Tm) of not more than 150° C.or outside the measurable range according to DSC measurement.

Also importantly, the elastomer (EL-4) for the polyolefin resincomposition of the present invention has a ratio of 1.0 mol % or less,preferably 0.5 mol % or less, and more preferably 0.2 mol % or less interms of irregularly bonded propylene monomers based on 2,1-insertion toall the propylene constituent units, and has a ratio of 1.0 mol % orless, preferably 0.5 mol % or less, and more preferably 0.2 mol % orless in terms of irregularly bonded α-olefin monomers based on2,1-insertion to all the α-olefin constituent units as determined from a¹³C-NMR spectrum.

When the elastomers (EL) have higher ratios of irregularly bondedpropylene and α-olefin monomers, mechanical strength properties of theresultant resin composition are deteriorated and the molded articlesexhibit poorer properties. Therefore, the ratios of irregularly bondedmonomer units desirably fall within the aforesaid limits.

The elastomers (EL) may be used singly or in combination of two or morekinds.

The elastomers (EL) may be prepared using the magnesium-supportedtitanium catalyst system or the metallocene catalyst system employed forsynthesis of the propylene polymer (PP-C). Preferably, the elastomers(EL) may be produced with a metallocene catalyst system that containsthe transition metal compound (1a).

In the present invention, the elastomers (EL) may be prepared by any ofliquid-phase polymerization, such as solution polymerization orsuspension polymerization, and gas-phase polymerization. Theliquid-phase polymerization may be conducted using an inert hydrocarbonsolvent. Exemplary inert hydrocarbon solvents include aliphatichydrocarbons, such as propane, butane, pentane, hexane, heptane, octane,decane, dodecane and kerosene; alicyclic hydrocarbons, such ascyclopentane, cyclohexane and methylcyclopentane; aromatic hydrocarbons,such as benzene, toluene and xylene; halogenated hydrocarbons, such asethylene chloride, chlorobenzene and dichloromethane; and mixturesthereof. The α-olefin to be polymerized may work as a solvent itself.

The temperature in the olefin polymerization is usually −50° C. orabove, preferably 40° C. or above, more preferably 50° C. or above, andeven more preferably 60° C. or above. Lower polymerization temperaturesresult to insufficient productivity and require additional steps forheat removal.

The polymerization pressure generally ranges from atmospheric pressureto 10 MPa (gauge pressure), preferably from atmospheric pressure to 5MPa (gauge pressure). The polymerization reaction can be carried outbatchwise, semi-continuously or continuously. Also, it is possible toconduct the polymerization in two or more stages under differentreaction conditions.

Hydrogen may be used in the polymerization to control the molecularweights of polymers or the polymerization activity, and its amount maybe suitably in the range of about 0.001 to 100 NL based on 1 kg of theolefin.

The elastomers (EL) may be used in an amount of 10 parts by weight ormore, preferably 20 parts by weight or more, and still preferably 30parts by weight or more based on 100 parts by weight of the propylenepolymer (PP-C). The polyolefin resin composition of the presentinvention can exhibit more superior mechanical strength properties,particularly flexural strength properties, when it contains theseelastomers in higher contents.

There is no particular limitation for the production of the polyolefinresin composition of the present invention, and any suitable processesmay be used. For example, the propylene polymer (PP-C) may be preparedfirst and consecutively the elastomers (EL) may be prepared. Thepolyolefin resin composition may also be obtained by preparing apropylene polymer (A2) with a metallocene catalyst and consecutivelyproducing the elastomers (EL), and adding a propylene polymer (A1)obtained with a catalyst system based on titanium tetrachloridesupported on magnesium chloride. Also, the propylene polymer (A1) andthe elastomers (EL) prepared as described above may be mixed to give thepolyolefin resin composition.

The polyolefin resin composition of the present invention may optionallycontain an inorganic filler (C) in addition to the propylene polymer(PP-C) and the elastomers (EL).

The inorganic fillers (C) for use in the present invention include talc,clays, calcium carbonate, mica, silicates, carbonates, glass fibers andbarium sulfate. Of these, talc and barium sulfate are preferred, andparticularly talc is preferable. The talc desirably ranges in meanparticle diameter from 1 to 5 μm, preferably from 1 to 3 μm. Theinorganic fillers (C) may be used singly or in combination of two ormore kinds.

The inorganic fillers (C) may be added in an amount of 1 to 50 parts byweight, preferably 2 to 40 parts by weight, and particularly preferably5 to 35 parts by weight based on 100 parts by weight of the polyolefinresin composition.

The polyolefin resin composition of the present invention, whichcomprises the propylene polymer (PP-C), the elastomers (EL) and theoptional inorganic filler (C) in the aforesaid weight ratios, exhibitsexcellent flow properties in molding and provides molded articles thathave an excellent balance among properties, including flexural modules,impact resistance, hardness, gloss and brittle temperature. Therefore,the resin composition according to the present invention can befavorably used as injection molding materials, and can produce injectionmolded articles while preventing flow marks.

The polyolefin resin composition of the present invention may optionallycontain further additives in addition to the propylene polymer (PP-C),the elastomers (EL) and the inorganic filler (C) without adverselyaffecting the objects of the invention. The additives include heatstabilizers, antistatic agents, weathering stabilizers, lightstabilizers, anti-aging agents, antioxidants, metal salts of fattyacids, softeners, dispersants, fillers, colorants, lubricants andpigments.

Exemplary antioxidants include conventional phenol-based, sulfur-basedand phosphorus-based antioxidants.

The antioxidants may be used singly or in combination of two or morekinds.

The antioxidants are desirably added in an amount of 0.01 to 1 part byweight, preferably 0.05 to 0.3 part by weight based on 100 parts byweight of the combined propylene polymer (PP-C), elastomers (EL) andoptional inorganic filler (C).

Exemplary light stabilizers include hindered amine light stabilizers(HALS) and ultraviolet light absorbers.

The hindered amine light stabilizers includetetrakis(1,2,2,6,6-pentamethyl-4-piperidine)-1,2,3,4-butanetetracarboxylate (molecular weight: 847), Adekastab™ LA-52 (molecularweight: 847), tetrakis(1,2,2,6,6-pentamethyl-4-piperidine)-1,2,3,4-butane tetracarboxylate),Adekastab™ LA-62 (molecular weight: about 900), Adekastab™ LA-67(molecular weight: about 900), Adekastab™ LA-63 (molecular weight: about2000), Adekastab™ LA-68LD (molecular weight: about 1900) (available fromASAHI DENKA CO., LTD.), and CHIMASSORB™ 944 (molecular weight: 72,500,available from Ciba Specialty Chemicals).

The ultraviolet light absorbers include TINUVIN™ 326 (molecular weight:316), TINUVIN™ 327 (molecular weight: 357) and TINUVIN™ 120 (molecularweight: 438) (available from Ciba Specialty Chemicals).

The light stabilizers may be used singly or in combination of two ormore kinds.

The hindered amine light stabilizers or the ultraviolet light absorbersare preferably used in an amount of 0.01 to 1 part by weight,particularly preferably 0.1 to 0.5 part by weight based on 100 parts byweight of the combined propylene polymer (PP-C), elastomers (EL) andoptional inorganic filler (C).

The metal salts of fatty acids neutralize the catalyst contained in thepolyolefin resin composition and also work as dispersant for the fillers(including the inorganic filler (C)) and pigments in the resincomposition. The metal salts of fatty acids enable the resin compositionto provide molded articles that have excellent properties, such as highstrength required for automobile interior trims.

Exemplary metal salts of fatty acids include calcium stearate (meltingpoint: 158° C.) and lithium stearate (melting point: 220° C.).

The metal salts of fatty acids are preferably added in an amount of 0.01to 1 part by weight, particularly preferably 0.05 to 0.5 part by weightbased on 100 parts by weight of the combined propylene polymer (PP-C),elastomers (EL) and optional inorganic filler (C). When the metal saltsof fatty acids have amounts within the above ranges, they caneffectively work as neutralizing agent and dispersant and also thesublimation level from the molded articles may be reduced.

The pigments may be those know in the art, and examples thereof includeinorganic pigments such as oxides, sulfides and sulfates of metals, andorganic pigments such as phthalocyanine pigments, quinacridone pigmentsand benzidine pigments.

The pigments are preferably added in an amount of 0.01 to 10 parts byweight, particularly preferably 0.05 to 2 parts by weight based on 100parts by weight of the combined propylene polymer (PP-C), elastomers(EL) and optional inorganic filler (C).

To produce the polyolefin resin composition of the present invention,the propylene polymer (PP-C), the elastomers (EL), the optionalinorganic filer (C) and additives may be mixed or melt kneaded with amixing equipment, such as a Banbury mixer, a single-screw extruder, atwin-screw extruder or a high-speed twin-screw extruder.

The specifically determined contents of the propylene polymer (PP-C) andthe elastomers (EL) enable the polyolefin resin composition of thepresent invention to exhibit excellent mechanical strength propertieswith good balance among tensile strength, flexural modules and impactresistance. Also, the polyolefin resin composition is capable ofproviding molded articles (including injection molded articles) thathave no or unnoticeable flow marks, high transparency and high gloss,which give them good appearance.

The injection molded articles according to the present invention may beobtained by injection molding the polyolefin resin composition, and havegood appearance and excellent mechanical strength properties. They havenumerous applications without limitation. Suitable uses thereof includeautomobile parts, such as automobile interior trims including door trimsand instrument panels, and automobile exterior trims including bumpersand mud guards; parts of home electric appliances, such as bodies of hotplates, rice cookers and pot, and washing machines; containers, such asbattery containers; and medical apparatus parts, such as injectionsyringes, ampules and Petri dishes.

The hollow vessels according to the present invention may bemanufactured by blow molding, expansion molding or vacuum forming thepolyolefin resin composition, and have exceptional appearance andexcellent mechanical strength properties. They may be used in numerousapplications without limitation, and, because of their superiortransparency and mechanical strength properties, can find suitableapplications as containers for solid detergents, liquid detergents, skinlotions, foods and drinking water.

The films or sheets according to the present invention may be producedby calendering, film casting or extrusion molding the polyolefin resincomposition, and have superior appearance, transparency and mechanicalstrength properties. They may be used in various applications withoutlimitation, and are suitably used as protective films or sheets due totheir high transparency, good appearance and excellent mechanicalstrength properties.

The fibers according to the present invention may be obtained by themelt spinning or other spinning technique for the polyolefin resincomposition, and have exceptional mechanical strength properties. Theymay be used in many applications without limitation, and are suitable tomake ropes and nonwoven fabrics.

EXAMPLES

The present invention will be described in more detail with reference tothe following examples, through the present invention should not berestricted by the examples.

Examples and Comparative Examples concerning to laminates prepared byusing a propylene/1-butene random copolymer (PBR), polypropylenecomposition (CC-1) or (CC-2), and polypropylene composition (CC-2) aredescribed hereinafter.

[Methods for Measuring Physical Properties]

[1-Butene Content]

The 1-butene content was determined by utilizing ¹³C-NMR.

[Intrinsic Viscosity [η]]

The intrinsic viscosity was measured in decalin at 135° C. and indicatedby dl/g.

[Molecular Weight Distribution (Mw/Mn)]

The molecular weight distribution (Mw/Mn) was measured using GPC-150Cmanufactured by Millipore Co., Ltd in the following manner.

As a separation column, TSK GNH HT was used. The column had a diameterof 27 mm and a length of 600 mm. The column temperature was set to 140°C. For a mobile phase, o-dichlorobenzene (Wako Pure Chemical Industries,Ltd.) and 0.025 wt % of BHT (manufactured by Takeda Chemical Industries,Ltd.) as an antioxidant were used. The mobile phase was moved at a rateof 1.0 ml/min and the specimen concentration was 0.1 wt %. The amount ofthe injected specimen was 500 μL and a differential refractometer wasused as a detector. As standard polystyrenes having a molecular weightof Mw<1000 and Mw>4×10⁶, polystyrenes manufactured by Tosoh Co., Ltdwere used, and as standard polystyrenes having a molecular weight of1000≦Mw≦4×10⁶, polystyrenes manufactured by Pressure Chemical Co., Ltdwere used.

[B Value]

The B value was determined in such a way that about 200 mg of acopolymer was homogeneously dissolved in 1 ml of hexachlorobutadiene ina 10 mmφ sample tube to prepare a specimen and the ¹³C-NMR spectrum ofthe specimen was usually measured under conditions of a measuringtemperature of 120° C., a measuring frequency of 25.05 MHz, a spectrumwidth of 1500 Hz, a filter width of 1500 Hz, a pulse repeating time of4.2 sec and an integrating time of 2000 to 5000 times, and from thespectrums, P₁, P₂ and P₁₂ (P₁ was an ethylene content fraction, P₂ was a1-butene content fraction and P₁₂ was a proportion of ethylene-1-butenechain in all the molecular chains were calculated.

[Triad Tacticity]

The ¹³C-NMR spectrum was measured using a hexachlorobutadiene solution(on the bases of tetramethylsilane) and the proportion of the area of apeak appeared at 21.0 to 21.9 ppm to all the area (100%) of peaksappeared at 19.5 to 21.9 ppm was determined.

[Proportion of Irregular Bond Based on 2,1-Insertion]

The proportion was determined utilizing a ¹³C-NMR spectrum with theabove-described method referring to Polymer, 30, 1350 (1989).

[Melting Point (TM)]

About 5 mg of a specimen was charged into an aluminum pan, heated to200° C. at a rate of 10° C./min, and maintained for 5 min at 200° C.Thereafter, the temperature was decreased to room temperature at a rateof 20° C./min and then elevated at a rate of 10° C./min. In elevatingthe temperature, the melting point was determined from an endothermiccurve. In the measurement, DSC-7 apparatus (manufactured by Perkin ElmerCo., Ltd) was used.

[Crystallinity]

A press sheet having a thickness of 1.0 mm was molded. After 24 hr fromthe molding, the crystallinity thereof was determined by X raydiffraction measurement.

[Crystallization Rate]

The ½ crystallizing time at 45° C. was determined using the above DSCapparatus.

[Tensile Test]

The tensile strength at yield point in a MD direction, elongation atbreak and initial modulus of elasticity were measured at a tensile rateof 200 m/min in accordance with JIS K6781.

[Heat-Seal Strength]

The test was conducted using the laminate films prepared in thefollowing examples as a specimen. The film was laid one on top the otherand heat-sealed at a pressure of 2 Kg/cm² for 1 sec by a seal bar havinga width of 5 mm at each temperatures, and then allowed to stand.

Subsequently, a 15 mm wide test piece was cut out from the specimen andwhen the heat-sealed part was peeled at a cross head speed of 200mm/min, the peeling strength was measured and the resulting value wastaken as heat-seal strength.

[Cloudiness (Haze)]

A film was formed in accordance with ASTM D1003 and aged in an air ovenset at 80° C. for 1 day. Before and after the aging, the cloudiness(haze) was measured.

[Blocking Resistance]

The blocking resistance was evaluated in accordance with ASTM D1893. Thespecimen film for measuring the heat-seal strength (1) was cut out totest pieces having a width of 10 cm and a length of 15 cm. The testpieces were laid one on top the other in such a way that the surfaces onwhich a polypropylene composition was laminated were faced each other.Then, the test pieces were sandwiched between two plates of glass toprepare a sample. A load of 20 Kg was put on it and the sample wasallowed to stand in an air oven at 50° C. After 3 days, the sample wastaken out and the peeling strength thereof was measured by a universaltesting machine and the resulting value was taken as a blocking value(N/m).

[Slip Properties]

The coefficient of static friction and the coefficient of dynamicfriction were measured in accordance with ASTM D1894.

The polypropylene and propylene/1-butene copolymer used in the examplesand comparative examples of the present invention are described below.In the examples and comparative examples of the present invention, thefollowing polypropylenes prepared by polymerizing with conventionalsolid titanium catalyst components were used as a polypropylene.

Polypropylene-1(PP-1): propylene random copolymer

-   (composition; propylene 96.4 mol %, ethylene 2.1 mol %, 1-butene 1.5    mol %, MFR (230° C.); 7.0 g/10 min, DSC melting point; 142° C.,    Crystallinity; 56%)    Polypropylene-2(PP-2): propylene random copolymer-   (composition; propylene 95.0 mol %, ethylene 3.5 mol %, 1-butene 1.5    mol %, MFR (230° C.); 1.5 g/10 min, DSC melting point; 140° C.,    Crystallinity; 52%)    Polypropylene-3(PP-3): propylene homopolymer-   (intrinsic viscosity [η]; 2.9 dl/g, DSC melting point; 164° C.,    Crystallinity; 62%)

In the next place, the preparation examples (examples) of thepropylene/1-butene copolymers (PBR) are described. The properties of thepropylene/1-butene random copolymers (PBR) prepared in the preparationexamples (examples) are shown in Table 2.

Example 1 Synthesis of PBR-1

In a 2000 ml polymerization reactor thoroughly purged with nitrogen, 900ml of dried hexane, 60 g of 1-butene and triisobutylaluminum (1.0 mmol)were charged at room temperature, the inside temperature of thepolymerization reactor was elevated to 70° C. and pressurized withpropylene to 0.7 Mpa. A toluene solution obtained by allowing 0.002 mmolof dimethylmethylene(3-tert-butyl-5-methylcyclopentadienyl)fluorenylzirconium dichloride to contact with 0.6 mmol in terms of aluminum ofmethyl aluminoxane (manufactured by Tosoh Fine chemical Co., Ltd) wasadded to the polymerization reactor. Polymerization was carried out for30 min while keeping an internal temperature of 70° C. and a propylenepressure of 0.7 Mpa and then 20 ml of methanol was added and thereby thepolymerization was ceased. After depressurization, a polymer wasprecipitated from the polymerization solution in 2 L of methanol, andwas dried in vacuo at 130° C. for 12 hr.

The polymer was obtained in an amount of 9.2 g. The polymer had amelting point of 80.6° C. and an intrinsic viscosity [η] of 1.18 dl/g.The physical properties of the resulting polymer were measured.

The results are shown in Table 2.

Example 2 Synthesis of PBR-2

The polymerization was carried out in the same procedure as Example 1except that 917 ml of hexane and 50 g of 1-butene were charged anddimethylmethylene(3-tert-butyl-5-methyl cyclopentadienyl)fluorenylzirconium dichloride was changed todiphenylmethylene(3-tert-butyl-5-methyl cyclopentadienyl)2,7-di-tert-butylfluorenyl zirconium dichloride.

The polymer was obtained in an amount of 11.5 g. The polymer had amelting point of 86.3° C. and an intrinsic viscosity [η] of 2.11 dl/g.The physical properties of the resulting polymer were measured. Theresults are shown in Table 2.

Example 3 Synthesis of PBR-3

The polymerization was carried out in the same procedure as Example 1except that 800 ml of hexane and 120 g of 1-butene were charged and theinternal temperature of the polymerization reactor was kept at 60° C.

The polymer was obtained in an amount of 10.8 g. The polymer had amelting point of 66.5° C. and an intrinsic viscosity [η] of 2.06 dl/g.The physical properties of the resulting polymer were measured. Theresults are shown in Table 2.

Comparative Example 1 Synthesis of PBR-C1

In a 2 L autoclave thoroughly purged with nitrogen, 830 ml of hexane,100 g of 1-butene and 1 mmol of triisobutylaluminum were charged and thetemperature was elevated to 70° C. and the total pressure was set to 0.7Mpa with feeding propylene. To the autoclave, 1 mmol of triethylaluminumand 0.005 mmol in terms of Ti atom of a titanium catalyst supported onmagnesium chloride were added. Polymerization was carried out for 30 minwhile keeping the total pressure of 0.7 Mpa by continuously feedingpropylene. Except for the above, the polymerization and the posttreatment were carried out in the same manner as Example 1.

The polymer was obtained in an amount of 33.7 g. The polymer had amelting point of 110.0° C. and an intrinsic viscosity [η] of 1.91 dl/g.The physical properties of the resulting polymer were measured.

The results are shown in Table 2.

Comparative Example 2 Synthesis of PBR-C2

In Comparative Example 2, 900 ml of hexane, 60 g of 1-butene and 1 mmolof triisobutylaluminum were charged and the temperature was elevated to70° C. and the total pressure was set to 0.7 Mpa with feeding propylene.0.30 mmol of methlaluminoxane and 0.001 mmol in terms of Zr atom ofrac-dimethylsilylene-bis{1-(2-methyl-4-phenyl-1-indenyl)}zirconiumdichloride were added to the autoclave. Polymerization was carried outfor 30 min while keeping the total pressure of 0.7 Mpa by continuouslyfeeding propylene. Except for the above, the polymerization and the posttreatment were carried out in the same procedure as Example 1.

The polymer was obtained in an amount of 39.7 g. The polymer had amelting point of 88.4° C. and an intrinsic viscosity [η] of 1.60 dl/g.

Comparative Example 3 Synthesis of PBR-C3

The polymerization was carried out in the same manner as ComparativeExample 2, except that 842 ml of hexane and 95 g of 1-butene werecharged. The polymer was obtained in an amount of 15.1 g. The polymerhad a melting point of 69.5° C. and an intrinsic viscosity [η] of 1.95dl/g. The physical properties of the resulting polymer were measured.The results are shown in Table 2.

With regard to the polymer of Example 3 and the polymer of ComparativeExample 3 which have the almost same melting point, the ½crystallization time at 45° C. was determined by DSC.

TABLE 2 Ex. 1 Ex. 2 Ex. 3 1-Butene content (mol %) 19.1 16.9 28.0Intrinsic viscosity [η] (dl/g) 1.18 2.11 2.06 Mw/Mn 2.04 2.09 2.15 Bvalue 1.01 1.05 1.04 Triad isotacticity (%) 96 96 95 Proportion ofirregular bond based on 0.1 0.1 0.2 2,1-insertion Melting point (° C.)80.6 86.3 66.5 146 exp(−0.022 M) 95.9 100.7 78.9 125 exp(−0.032 M) 67.872.8 51.0 146 exp(−0.0265 M) 88.0 93.3 69.5 ½ crystallization time (min)5.2 1-Butene content (mol %) 23.1 26.4 34.5 Intrinsic viscosity [η](dl/g) 1.91 1.60 1.95 Mw/Mn 3.40 2.05 2.03 B value 0.92 1.00 1.15 Triadisotacticity (%) 99 99 99 Proportion of irregular bond based on <0.010.02 0.1 2,1-insertion Melting point (° C.) 110.0 88.4 69.5 146exp(−0.022 M) 87.8 81.7 68.3 125 exp(−0.032 M) 59.7 53.7 41.4 146exp(−0.0265 M) 79.2 72.5 58.5 ½ crystallization time (min) 33.1

Example 4

In an air-knife system cast-molding machine equipped with an extruderhaving a screw diameter of 40 mm and a T-die having a width of 400 mm,70 wt % of polypropylene-1 and 30 wt % of the propylene/1-butene randomcopolymer prepared in Example 1 were fed and a film having a thicknessof 50 μm was molded in conditions that the resin temperature was 230° C.and the chilling temperature was 30° C. The mechanical properties andthe heat-seal properties of the resulting film are shown in Table 3.

Examples 5 and 6, Comparative Example 4 to 6

In each example, the procedure of Example 4 was repeated except forusing the propylene/1-butene random copolymer as described in Table 3,to prepare a film. The evaluation results of the resulting film areshown in Table 3.

TABLE 3 Com. Com. Com. Ex. 4 Ex. 5 Ex. 6 Ex. 4 Ex. 5 Ex. 6 Resincomposition PP-1 % 70 70 70 70 70 70 PBR-1 % 30 PBR-2 % 30 PBR-3 % 30PBR-C1 % 30 PBR-C2 % 30 PBR-C3 % 30 Tensile test Yield stress MPa 14 1513 15 15 14 Elongation at break % 650 650 650 650 650 650 Initialmodulus of elasticity MPa 490 530 430 590 570 490 Haze % 2.0 1.8 1.6 1.82.6 2.4 Haze % (80° C. × 1 day) 2.1 1.8 1.6 3.9 2.7 2.5 Blockingresistance N/m 0.2 0.2 0.2 0.6 0.2 0.2 Slip properties Static 0.63 0.600.68 0.82 0.65 0.74 Dynamic 0.51 0.46 0.54 0.74 0.59 0.60

Example 7

In this example, a composition of 50 wt % of propylene/1-butene randomcopolymer (PBR-3) prepared in Example 3 and 50 wt % of polypropylene-2(PP-2) was palletized with a single-screw extruder of 40 mmφ. The pelletwas fed to a cast-molding machine equipped with a dice having a width of300 mm and a sheet having a thickness of 250 μm was prepared at a resintemperature of 230° C. Further, the resulting sheet was cut out intosquares having a size of 9 cm and the square was orientated 5 times in aMD direction using a desk stretching-machine. The shrinkage factor ofthe resulting orientated film was measured in the following method. Theresults are shown in Table 4.

[Shrinkage Factor]

A stretched film was slit to prepare a sample having a size of 15 mm×150mm (stretching direction). The sample was immersed in a hot water at 90°C. for 10 sec and the shrinkage factor was determined from the lengthshrunk and the length before shrinking.

Comparative Examples 7 and 8

In each example, the procedure of Example 7 was repeated except forusing a propylene/1-butene random copolymer having the composition asdescribed in Table 4, to prepare a stretched film. The evaluationresults of the resulting stretched film are shown in Table 4.

TABLE 4 Ex. 7 Com. Ex. 7 Com. Ex. 8 Resin composition PP-2 % 50 50 50PBR-3 % 50 PBR-C1 % 50 PBR-C3 % 50 Shrinkage Factor (%) 32 25 28

Example 1b

Using an air knife system two-kind three-layer cast molding machineequipped with an extruder (for core layer) having a screw diameter of 30mm, an extruder (for both sealant layers) having a screw diameter of 25mm and a T-die having a width of 200 mm, a sample of an unstretchedsheet as shown in FIG. 1 was prepared. The core layer comprisespolypropylene-3 (PP-3). Both of the sealant layers comprise 75 wt partsof polypropylene-1 (PP-1), 25 wt parts of PBR-2 and, based on the totalamount (100 wt parts) of PP-1 and PBR-2, 0.1 wt parts of ananti-blocking agent. In this sheet, the core layer had a thickness of600 μm and the sealant layers both have a thickness of 80 μm.

The resulting unstretched sheet sample was cut into a square having asize of 10 cm, and the sample was stretched in 5×8 times using a batchbiaxial stretching machine to prepare a biaxially stretched film havinga thickness of 22 to 24 μm. The stretching was carried out in conditionssuch that the preheating time was 2 min, the stretching temperature was160° C., and the annealing time for the film after stretching was 2 min.The physical properties of the film are shown in Table 5.

Example 2b

The procedure of Example 1b was repeated except that PBR-3 was usedinstead of PBR-2 used in both of the sealant layers in Example 1b toprepare a biaxially stretched film having a thickness of about 22 to 24μm. The physical properties of the film are shown in Table 5.

Example 3b

The procedure of Example 2b was repeated except that 50 wt parts ofpolypropylene-1 and 50 wt parts of PBR-3 were used to prepare abiaxially stretched film having a thickness of about 22 to 24 μm. Thephysical properties of the film are shown in Table 5.

Comparative Example 1b

The procedure of Example 1b was repeated except that PBR-C1 was usedinstead of PBR-2 used in both of the sealant layers to prepare abiaxially stretched film having a thickness of about 22 to 24 μm. Thephysical properties of the film are shown in Table 5.

Comparative Example 2b

The procedure of Example 1b was repeated except that PBR-C2 was usedinstead of PBR-2 used in both of the sealant layers to prepare abiaxially stretched film having a thickness of about 22 to 24 μm. Thephysical properties of the film are shown in Table 5.

Comparative Example 3b

The procedure of Example 1b was repeated except that PBR-C3 was usedinstead of PBR-2 used in both of the sealant layers to prepare abiaxially stretched film having a thickness of about 22 to 24 μm. Thephysical properties of the film are shown in Table 5.

Comparative Example 4b

The procedure of Comparative Example 3b was repeated except that 50 wtparts of polypropylene-1 and 50 wt parts of PBR-C3 were used to preparea biaxially stretched film having a thickness of about 22 to 24 μm. Thephysical properties of the film are shown in Table 5.

In the biaxially stretched films prepared using the propylene/1-butenerandom copolymer (PBR-2,3) according to the present invention, thetemperature at which the heat-seal strength reached 2 (N/15 mm) was nothigher than 90° C. so that the films obtained had remarkably excellentlow temperature heat-sealability as compared with Comparative Example1b. The films had good blocking resistance and excellent balance betweenlow temperature heat-sealability and blocking resistance.

Furthermore, the propylene/1-butene random copolymer (PBR-2,3) used inthe present invention had a relatively higher crystallization rate ascompared with the propylene/1-butene random copolymer (PBR-C2, C3)having the same melting point as PBR-2,3, used in Comparative Examplesso that the biaxially stretched films prepared using PBR-2,3 hadexcellent hot tack properties and transparency.

TABLE 5 Example 1b 2b 3b Polypropylene-1 (wt part) 75 75 50 PBR-2 (wtpart) 25 PBR-3 (wt part) 25 50 Cloudiness (Haze) (%) 11.0 13.2 13.9Cloudiness change with time (%) 13.3 14.3 14.0 Slip properties/Staticfriction 0.8 0.8 0.8 Slip properties/Dynamic friction 0.6 0.6 0.7Blocking resistance (N/m) 0.14 0.14 0.27 Heat seal strength (N/15 mm) 65° C. 0 0.3  70° C. 0 0.3 3.1  80° C. 0.1 2.1 3.3  90° C. 2.6 3.5 3.2100° C. 3.7 3.7 3.4 110° C. 3.6 3.6 120° C. 3.6 Hot tack properties (mm) 80° C. 300 255  90° C. 300 220 100 100° C. 210 120 40 110° C. 125 60 15120° C. 40 25 15 130° C. 20 15 140° C. 15 15 Comparative Example 1b 2b3b 4b Polypropylene-1 (wt part) 75 75 75 50 PBR-C1 (wt part) 25 PBR-C2(wt part) 25 PBR-C3 (wt part) 25 50 Cloudiness (Haze) (%) 13.5 15.4 23.725.9 Cloudiness change with time (%) 17.3 17.2 26.6 27.9 Slipproperties/Static friction 0.7 0.8 0.9 0.9 Slip properties/Dynamicfriction 0.6 0.6 0.7 0.7 Blocking resistance (N/m) 0.15 0.13 0.14 0.26Heat seal strength (N/15 mm)  65° C. 0 0.3  70° C. 0.2 2.9  80° C. 0 02.3 3.5  90° C. 0.2 2.3 3.3 3.4 100° C. 2.4 3.4 3.3 3.4 110° C. 3.3 3.63.4 120° C. 3.5 3.6 130° C. 3.8 Hot tack properties (mm)  80° C. 300 90° C. 300 300 270 100° C. 300 260 185 115 110° C. 200 155 120 60 120°C. 150 45 75 35 130° C. 70 20 20 20 140° C. 20 15 20

The examples and comparative examples concerning to the transition metalcompound of the formula (2a) and the catalysts and polymerizations usingthe transition metal compound are described below.

Measuring Methods of Physical Properties

[Ethylene Content in Polymer]

Using a Fourier transform infrared spectrophotometer FT/IR-610manufactured by JASCO Inc., the area at about 1155 cm⁻¹ in a rockingvibration based on methyl group of propylene and the absorbance at about4325 cm⁻¹ in a overtone absorption caused by C—H stretching vibrationwere determined and from the ratio thereof, the ethylene content in thepolymer was calculated by an analysis curve (prepared using a standardspecimen standardized by ¹³C-NMR).

[Intrinsic Viscosity [η]]

Using an automatic dynamic viscosity-measuring apparatus VMR-053PCmanufactured by Rigo Co., Ltd. and an improved Ubbellohde capillaryviscometer, a specific viscosity η sp in decalin at 135° C. wasdetermined and the intrinsic viscosity was calculated from the followingformula.[η]=ηsp/{C(1+K·ηsp)}(C: solution concentration [g/dl], K: constant)[Weight average molecular weight (Mw), Number average molecular weight(Mn)]

Using Alliance GPC2000 manufactured by Waters Co, the measurement wascarried out by moving 500 μl of a specimen solution having aconcentration of 0.1 wt % at a flow rate of 1.0 ml/min. As standardpolystyrene, one manufactured by Tosoh Co. was used and the molecularweight was determined as a molecular weight converted to each polymer.

-   Separation column: TSK gel GMH6-HT and TSK gel GMH6-HTL each having    two columns of an inner diameter of 7.5 mm and a length of 300 mm-   Column temperature: 140° C.-   Mobile phase: o-dichlorobenzene-   Detector: Differential refractometer    [Melting Point (Tm)]

Using Pyris 1 manufactured by Perkin Elmer Co., about 5 mg of a specimenwas heated to 200° C. in a nitrogen atmosphere (20 ml/min) andmaintained for 10 min. Thereafter, the specimen was cooled to 30° C. ata rate of 10° C./min and maintained at 30° C. for 5 min. Successively,when the specimen was heated to 200° C. at a rate of 10° C./min, themelting point was determined from the peak point of the crystal-meltingpeak.

The structures of the compounds obtained in the following synthesisexamples were determined by 270 MHz ¹H-NMR (JEOL GSH-270), FD-Massspectrometry (JEOL SX-102A) and the like.

Example 1c Synthesis ofdiphenylmethylene(3-tert-butyl-5-methyl-cyclopentadienyl)(fluorenyl)zirconium dichloride

(1) Synthesis of 3-tert-butyl-1-methyl-6,6-diphenyl fulvene

In a 200 ml three-necked flask equipped with a magnetic stirrer chip andthree-way cock thoroughly purged with nitrogen, 2.73 g of3-tert-butyl-1-methyl-cyclopentadiene (20.1 mmol) was dissolved in 30 mlof dehydrated tetrahydrofuran in a nitrogen atmosphere. To the solution,13.5 ml of n-butyl lithium/hexane solution (1.58M: 21.3 mmol) wasgradually added dropwise in an ice bath and stirred at room temperaturefor 3 days. To the reaction solution, 10.5 ml of hexamethylphosphoramide (60.4 mmol) was added and stirred at room temperature for1 hr. To the solution, a solution prepared by dissolving 3.87 g ofbenzophenone (21.2 mmol) in 40 ml of dehydrated tetrahydrofuran wasgradually added dropwise in an ice bath and stirred at room temperatureover night. To the resulting reaction mixture, 50 ml of a hydrochloricacid aqueous solution (1N) was gradually added dropwise in an ice bathand stirred at room temperature for some time. Diethyl ether was addedto the mixed solution to separate an organic phase. The organic phasewas washed with a saturated sodium bicarbonate aqueous solution, waterand saturated brine. The organic phase was dried with anhydrousmagnesium sulfate, thereafter the drying agent was filtered off and thesolvent was distilled off from the filtrate under reduced pressure togive a dark-red liquid. The liquid was purified with a columnchromatography using 300 g of silica gel (developing solvent: n-hexane)and the developing solvent was distilled off under reduced pressure, andthereby the aimed compound was obtained in an amount of 3.28 g (10.9mmol) as a reddish-orange solid (yield: 54%).

(2) Synthesis of(3-tert-butyl-5-methyl-cyclopentadienyl)(fluorenyl)diphenylmethane

In a 200 ml three-necked flask equipped with a magnetic stirrer chip andthree-way cock thoroughly purged with nitrogen, 1.75 g of fluorene (10.5mmol) was dissolved in 40 ml of dehydrated diethylether in a nitrogenatmosphere. To the solution, 7.0 ml of an n-butyl lithium/hexanesolution (1.58M: 11.1 mmol) was gradually added dropwise in an ice bathand stirred at room temperature over night. The solvent was distilledoff under reduced pressure and thereby a reddish orange solid wasobtained. In a glove box, to the reddish-orange solid, 3.17 g of3-tert-butyl-1-methyl-6,6-diphenylfulvene (10.6 mmol) was added anddissolved in 50 ml of dehydrated diethyl ether. The solution was stirredfor 120 hr while intermittent refluxing in a 50° C. oil bath and stirredat room temperature for 496 hr. To the resulting reaction mixture, 50 mlof a distilled water was gradually added dropwise in an ice bath anddiethyl ether was added to the mixed solution to separate an organicphase. The organic phase was washed with distilled waster and saturatedbrine. The organic phase was dried with anhydrous magnesium sulfate,thereafter the drying agent was filtered off and the solvent wasdistilled off from the filtrate under reduced pressure to give red oil.The red oil was re-crystallized from ethanol and dried under reducedpressure, and thereby the aimed compound was obtained in an amount of0.648 g (1.39 mmol) as a pale yellow solid (yield: 13%).

(3) Synthesis ofdiphenylmethylene(3-tert-butyl-5-methyl-cyclopentadienyl)(fluorenyl)zirconiumdichloride

In a 200 ml three-necked flask equipped with a magnetic stirrer chip andthree-way cock thoroughly purged with nitrogen, 0.642 g of(3-tert-butyl-5-methyl-cyclopentadienyl)(fluorenyl)diphenyl methane(1.38 mmol) was dissolved in 40 ml of dehydrated diethylether in anitrogen atmosphere. To the solution, 1.85 ml of a n-butyllithium/hexane solution (1.58M: 2.92 mmol) was gradually added dropwiseat room temperature. The solution was stirred with refluxing for 6 hrand thereafter stirred at room temperature over night. The solvent wasdistilled off under reduced pressure to give a reddish-orange solid. Ina glove box, 0.325 g of zirconium tetrachloride (1.39 mmol) was added tothe solid and cooled in a dry ice/methanol bath. To the reactionmixture, 50 ml of dehydrated diethyl ether sufficiently cooled in a dryice/methanol bath was transported through a cannular tube and stirredfor 4 days while gradually returning the temperature to roomtemperature. The reaction mixture was introduced into the glove box andthe solvent was distilled off under reduced pressure. The residualproduct was re-slurried with 50 ml of dehydrated hexane and filtered offusing a glass filter filled with diatomaceous earth. The filtrate wasconcentrated to prepare a solid and the solid was washed with dehydrateddiethyl ether and dried under reduced pressure, and thereby the aimedcompound was obtained in an amount of 35 mg (0.056 mmol) as areddish-pink solid.

Furthermore, the reddish-orange solid remained on the filter was washedwith a small amount of dichloromethane and the solvent was distilled offunder reduced pressure from the filtrate. The resulting reddish-brownsolid was washed with a small amount of diethyl ether and dried underreduced pressure, and thereby the aimed compound was obtained in anamount of 11 mg (0.018 mmol) as a reddish-pink solid (yield: 5%). Theidentification was carried out by ¹H-NMR spectrum and FD-massspectrometry spectrum. The measurement results are shown below.

¹H-NMR spectrum (CDCl₃, TMS standard): /ppm 1.10 (s, 9H), 1.90 (s, 3H),5.68 (d, 1H), 6.19 (d, 1H), 6.18-6.31 (m, 1H), 6.87-6.93 (m, 1H),6.98-7.09 (m, 2H), 7.20-7.55 (m, 8H), 7.77-7.81 (m, 1H), 7.90-7.95 (m,3H), 8.11-8.15 (m, 2H) FD-mass spectrometry spectrum: M/z=626 (M⁺)

Example 2c Synthesis ofdiphenylmethylene(3-tert-butyl-5-methyl-cyclopentadienyl)(3,6-di-tert-butyl-fluorenyl)zirconium dichloride

(1) Synthesis of (3-tert-butyl-5-methyl-cyclopentadienyl)(3,6-di-tert-butyl-fluorenyl)diphenylmethane

In a 200 ml three-necked flask equipped with a magnetic stirrer chip andthree-way cock thoroughly purged with nitrogen, 3.01 g of3,6-di-tert-butyl-fluorene (10.8 mmol) was dissolved in 80 ml ofdehydrated diethyl ether in a nitrogen atmosphere. To the solution, 7.6ml of a n-butyl lithium/hexane solution (1.56M: 11.9 mmol) was graduallyadded dropwise in an ice bath and stirred at room temperature overnight. To the reaction solution, 50 ml of a solution prepared bydissolving 4.86 g of 3-tert-butyl-1-methyl-6,6-diphenyl fulvene (16.2mmol) in 50 ml of dehydrated diethyl ether was added and stirred withrefluxing for 13 days. To the reaction mixture, 30 ml of distilled waterwas gradually added dropwise in an ice bath, and thereafter diethylether was added to separate an organic phase. The organic phase waswashed with distilled water and saturated brine. The organic phase wasdried with anhydrous magnesium sulfate, thereafter the drying agent wasfiltered off and the solvent was distilled off from the filtrate underreduced pressure to give red solid. The red solid was re-crystallizedusing ethanol and dried under reduced pressure, and thereby the aimedcompound was obtained in an amount of 4.42 g (7.63 mmol) as a paleyellow solid (yield: 71%).

(2) Synthesis ofdiphenylmethylene(3-tert-butyl-5-methyl-cyclopentadienyl)(3,6-di-tert-butyl-fluorenyl)zirconiumdichloride

In a 50 ml Schlenk flask equipped with a magnetic stirrer chip andthree-way cock thoroughly purged with nitrogen, 1.42 g of(3-tert-butyl-5-methyl-cyclopentadienyl)(3,6-di-tert-butyl-fluorenyl)diphenyl methane (2.45mmol) was dissolved in 30 ml of dehydrated diethyl ether in a nitrogenatmosphere. To the solution, 5.0 ml of a n-butyl lithium/hexane solution(1.56M: 7.80 mmol) was gradually added dropwise in an ice bath andthereafter stirred at room temperature for two days. The solvent wasdistilled off under reduced pressure to give a pale orange solid. Thepale orange solid was washed with dehydrated pentane and dried underreduced pressure to prepare a pale orange solid. To the solid, 30 ml ofdehydrated diethyl ether was added and sufficiently cooled by a dryice/methanol bath, and then 0.515 g of zirconium tetrachloride (2.21mmol) was added. The mixture was stirred for 3 days while graduallyreturning the temperature to room temperature and thereafter the solventwas distilled off. The reaction mixture was introduced into a glove boxand was re-slurried with dehydrated pentane and filtered using a glassfilter filled with diatomaceous earth. The filtrate was concentrated toprepare a solid and the solid was washed with a small amount ofdehydrated toluene and dried under reduced pressure, and thereby theaimed compound was obtained in an amount of 894 mg (1.21 mmol) as areddish-pink solid (yield: 49%).

The identification was carried out by ¹H-NMR spectrum and FD-massspectrometry spectrum. The measurement results are shown below.

¹H-NMR spectrum (CDCl₃, TMS standard): /ppm 1.11 (s, 9H), 1.41 (s, 9H),1.42 (s, 9H), 1.88 (s, 3H), 5.62 (d, 1H), 6.12 (d, 1H), 6.17-6.21 (m,1H), 6.95-7.02 (m, 2H), 7.10-7.45 (m, 7H), 7.79-7.82 (m, 2H), 7.91-7.97(m, 3H), 8.04-8.07 (m, 2H) FD-mass spectrometry spectrum: M/z=738 (M⁺)

Example 3c Synthesis ofdiphenylmethylene(3-tert-butyl-5-methyl-cyclopentadienyl)(2,7-di-tert-butyl-fluorenyl)zirconium dichloride

(1) Synthesis of (3-tert-butyl-5-methyl-cyclopentadienyl)(2,7-di-tert-butyl-fluorenyl)diphenylmethane

In a 200 ml three-necked flask equipped with a magnetic stirrer chip andthree-way cock thoroughly purged with nitrogen, 2.53 g of2,7-di-tert-butyl-fluorene (9.10 mmol) was dissolved in 70 ml ofdehydrated diethyl ether in a nitrogen atmosphere. To the solution, 6.4ml of a n-butyl lithium/hexane solution (1.56M: 9.98 mmol) was graduallyadded dropwise in an ice bath and stirred at room temperature overnight. To the reaction solution, a solution prepared by dissolving 3.01g of 3-tert-butyl-1-methyl-6,6-diphenyl fulvene (10.0 mmol) in 40 ml ofdehydrated diethyl ether was added and stirred with refluxing for 7days. The reaction mixture was added to 100 ml of a hydrochloric acidaqueous solution (1N) and thereafter diethyl ether was added to separatean organic phase. The organic phase was washed with a saturated sodiumbicarbonate aqueous solution and saturated brine. The organic phase wasdried with anhydrous magnesium sulfate, thereafter the drying agent wasfiltered off and the solvent was distilled off from the filtrate underreduced pressure to give a reddish-brown liquid. The liquid was purifiedby a column chromatography using 180 g of silica gel (developingsolvent: n-hexane) and the developing solvent was distilled off underreduced pressure. The remainder was re-crystallized using methanol anddried under reduced pressure, and thereby the aimed compound wasobtained in an amount of 1.65 g (2.85 mmol) as a pale yellow solid(yield: 31%).

(2) Synthesis ofdiphenylmethylene(3-tert-butyl-5-methyl-cyclopentadienyl)(2,7-di-tert-butyl-fluorenyl)zirconiumdichloride

In a 50 ml Schlenk flask equipped with a magnetic stirrer chip andthree-way cock thoroughly purged with nitrogen, 0.502 g of(3-tert-butyl-5-methyl -cyclopentadienyl)(2,7-di-tert-butyl-fluorenyl)diphenyl methane (0.868 mmol) was dissolvedin 30 ml of dehydrated diethylether in a nitrogen atmosphere. To thesolution, 1.40 ml of a n-butyl lithium/hexane solution (1.56M: 2.18mmol) was gradually added dropwise in an ice bath and thereafter stirredat room temperature over night. The solvent was distilled off underreduced pressure to give an orange solid. The orange solid was washedwith dehydrated pentane and dried under reduced pressure to prepare anorange solid. To the solid, 30 ml of dehydrated diethyl ether was addedand sufficiently cooled by a dry ice/methanol bath, and then 0.206 g ofzirconium tetrachloride (0.882 mmol) was added. The mixture was stirredfor 2 days while gradually returning the temperature to room temperatureand thereafter the solvent was distilled off under reduced pressure. Thereaction mixture was introduced into a glove box and was re-slurriedwith dehydrated hexane and filtered using a glass filter filled withdiatomaceous earth. The filtrate was concentrated to prepare a solid andthe solid was washed with a small amount of dehydrated toluene and driedunder reduced pressure, and thereby the aimed compound was obtained inan amount of 140 mg (0.189 mmol) as a pink solid (yield: 22%).

The identification was carried out by ¹H-NMR spectrum and FD-massspectrometry spectrum. The measurement results are shown below.

¹H-NMR spectrum (CDCl₃, TMS standard): □/ppm 0.99 (s, 9H), 1.09 (s, 9H),1.12 (s, 9H), 1.91 (s, 3H), 5.65 (d, 1H), 6.14 (d, 1H), 6.23 (m, 1H),7.03 (m, 1H), 7.18-7.46 (m, 6H), 7.54-7.69 (m, 2H), 7.80-7.83 (m, 1H),7.95-8.02 (m, 5H) FD-mass spectrometry spectrum: M/z=738 (M⁺)

Example 4c Synthesis of di(p-tolyl)methylene(3-tert-butyl-5-methyl-cyclopentadienyl)(fluorenyl)zirconium dichloride

(1) Synthesis of 3-tert-butyl-1-methyl-6,6-di-(p-tolyl)fulvene

In a 200 ml three-necked flask equipped with a magnetic stirrer chip andthree-way cock thoroughly purged with nitrogen, 1.56 g of powderypotassium hydroxide (27.8 mmol) and 100 ml of dehydrated dimethoxyethane were added in a nitrogen atmosphere. To the suspension, 2.46 g of3-tert-butyl-1-methyl-cyclopentadiene (18.0 mmol) was gradually addeddropwise at room temperature and stirred under reflux for 2 hr. To thereaction solution, a solution prepared by dissolving 3.99 g of4,4′-dimethylbenzophenone (19.0 mmol) in 40 ml of dehydrated dimethoxyethane was gradually added and stirred under reflux for 3 days. To thereaction mixture, 50 ml of a hydrochloric acid aqueous solution (1N) wasgradually added dropwise in an ice bath, and stirred at room temperaturefor some time. The organic phase was separated by adding diethyl etherand washed with a saturated sodium bicarbonate aqueous solution, waterand saturated brine. The organic phase was dried with anhydrousmagnesium sulfate, and thereafter the drying agent was filtered off andthe solvent was distilled off from the filtrate under reduced pressureto give a dark red liquid. The liquid was purified by a columnchromatography using 170 g of silica gel (developing solvent: n-hexane)and the developing solvent was distilled off under reduced pressure, andthereby the aimed compound was obtained in an amount of 2.55 g (7.76mmol) as a red solid (yield: 43%).

(2) Synthesis of(3-tert-butyl-5-methyl-cyclopentadienyl)(fluorenyl)di(p-tolyl)methane

In a 200 ml three-necked flask equipped with a magnetic stirrer chip andthree-way cock thoroughly purged with nitrogen, 0.373 g of fluorene(2.25 mmol) was dissolved in 60 ml of dehydrated diethylether in anitrogen atmosphere. To the reaction solution, 1.6 ml of a n-butyllithium/hexane solution (1.56M: 2.50 mmol) was gradually added dropwisein an ice bath and thereafter stirred at room temperature over night. Tothe reaction solution, a solution prepared by dissolving 1.10 g of3-tert-butyl-1-methyl-6,6-di(p-tolyl)fulvene (3.36 mmol) in 60 ml ofdehydrated diethyl ether was added and stirred under reflux for 10 days.To the reaction mixture, 30 ml of distilled water was gradually addeddropwise in an ice bath, and thereafter the organic layer was separatedby adding diethyl ether and washed with distilled water and saturatedbrine. The organic phase was dried with anhydrous magnesium sulfate andthen the drying agent was filtered off. The solvent was distilled offfrom the filtrate under reduced pressure to give a red brown liquid. Thered brown liquid was purified by a column chromatography using 80 g ofsilica gel (developing solvent: n-hexane) and the developing solvent wasdistilled off under reduced pressure. The residue product wasre-crystallized using hexane and dried under reduced pressure, andthereby the aimed compound was obtained in an amount of 0.140 g (0.282mmol) as a pale yellow solid (yield: 13%).

(3) Synthesis of di(p-tolyl)methylene(3-tert-butyl-5-methyl-cyclopentadienyl)(fluorenyl)zirconium dichloride

In a 100 ml Schlenk flask equipped with a magnetic stirrer chip andthree-way cock thoroughly purged with nitrogen, 0.496 g of(3-tert-butyl-5-methyl-cyclopentadienyl)(fluorenyl)di(p-tolyl)methane(1.00 mmol) was dissolved in 20 ml of dehydrated diethylether in anitrogen atmosphere. To the solution, 1.35 ml of a n-butyllithium/hexane solution (1.58M: 2.13 mmol) was gradually added dropwisein an ice bath, and thereafter stirred at room temperature over night.The reaction solution was sufficiently cooled in a dry ice/methanol bathand then 0.231 g of zirconium tetrachloride (0.990 mmol) was added. Thesolution was stirred for 4 days while gradually returning thetemperature to room temperature, and thereafter the solvent wasdistilled off under reduced pressure. The reaction mixture wasintroduced into a glove box and re-slurried with dehydrated pentane andthen filtered with a glass filter filled with diatomaceous earth. Thefiltrate was concentrated to prepare a solid, and the solid was washedwith a small amount of dehydrated diethyl ether and dried under reducedpressure and thereby the aimed compound was obtained as a reddish-pinksolid.

Furthermore, the pink solid remained on the filter was washed with asmall amount of dichloromethane and the solvent was distilled off underreduced pressure from the filtrate. The resulting reddish-pink solid waswashed with a small amount of diethyl ether and dried under reducedpressure, and thereby the aimed compound was obtained as a reddish-pinksolid. The aimed compound was obtained in a total amount of 222 mg(0.340 mmol) (yield: 34%). The identification was carried out by ¹H-NMRspectrum and FD-mass spectrometry spectrum. The measurement results areshown below.

¹H-NMR spectrum (CDCl₃, TMS standard): /ppm 1.09 (s, 9H), 1.90 (s, 3H),2.32 (s, 6H), 5.67 (d, 1H), 6.17 (d, 1H), 6.34-6.37 (m, 1H), 6.88-6.93(m, 1H), 6.98-7.24 (m, 6H), 7.46-7.53 (m, 2H), 7.62-7.66 (m, 1H),7.76-7.80 (m, 3H), 8.10-8.14 (m, 2H) FD-mass spectrometry spectrum:M/z=654 (M⁺)

Comparative Example 1C Synthesis ofdiphenylmethylene(3-tert-butyl-cyclopentadienyl)(fluorenyl)zirconiumdichloride

(1) Synthesis of 2-tert-butyl-6,6-diphenyl fulvene

In a 300 ml three-necked flask equipped with a magnetic stirrer andthree-way cock was thoroughly purged with nitrogen, 4.75 g of3-tert-butyl-cyclopentadiene (38.9 mmol) was dissolved in 100 ml ofdehydrated tetrahydrofuran in a nitrogen atmosphere. To the solution, 26ml of n-butyl lithium/hexane solution (1.58M: 41.1 mmol) was graduallyadded dropwise in an ice bath and stirred at room temperature overnight. To the reaction solution, 21 ml of hexamethyl phosphoramide (121mmol) dried with molecular sieves 4A was added in the ice bath andfurther stirred at room temperature for 1 hr. To the solution, asolution prepared by dissolving 10.2 g of benzophenone (56.0 mmol) to 30ml of dehydrated tetrahydrofuran was gradually added dropwise in an icebath and stirred at room temperature 1 day. To the resulting reactionmixture, 100 ml of a hydrochloric acid aqueous solution (5%) was added.Thereafter, hexane was added to the mixed solution to separate anorganic phase. The organic phase was washed with water and saturatedbrine. The organic phase was dried with anhydrous magnesium sulfate,thereafter the drying agent was filtered off and the solvent wasdistilled off from the filtrate under reduced pressure to givedark-brown oil. The oil was purified with a column chromatography using400 g of silica gel (developing solvent: n-hexane) and the developingsolvent was distilled off under reduced pressure, and thereby the aimedcompound was obtained in an amount of 4.42 g (15.4 mmol) as an orangesolid (yield: 40%).

(2) Synthesis of(3-tert-butyl-cyclopentadienyl)(fluorenyl)diphenylmethane

In a 200 ml three-necked flask equipped with a magnetic stirrer chip andthree-way cock thoroughly purged with nitrogen, 0.76 g of fluorene (4.57mmol) was dissolved in 40 ml of dehydrated diethyl ether in a nitrogenatmosphere. To the solution, 3.1 ml of a n-butyl lithium/hexane solution(1.57M: 4.87 mmol) was gradually added dropwise in an ice bath andstirred at room temperature for over night. The solvent was distilledoff under reduced pressure and thereby a reddish-orange solid wasobtained. To the solid, a solution prepared by dissolving 2.40 g of2-tert-butyl-6,6-diphenyl fulvene (8.38 mmol) in 150 ml of dehydrateddiethyl ether was added and stirred under reflux for 7 days. Thereaction mixture was added to 150 ml of a hydrochloric acid aqueoussolution (2%) and then diethyl ether was added therein to separate anorganic phase. The organic phase was washed with water and saturatedbrine. The organic phase was dried with anhydrous magnesium sulfate andthe drying agent was filtered off. The solvent was distilled off underreduced pressure from the filtrate and thereby orange brown oil wasobtained. The oil was re-crystallized using hexane and thereby the aimedcompound was obtained in an amount of 1.03 g (2.28 mmol) as a paleyellow solid. The solid further was purified with a chromatography using100 g of silica gel (developing solvent: n-hexane) and the developingsolvent was distilled off under reduced pressure and thereby the aimedcompound was obtained in an amount of 0.370 g (0.817 mmol) as a yellowsolid (yield: 67%).

(3) Synthesis ofdiphenylmethylene(3-tert-butyl-cyclopentadienyl)(fluorenyl) zirconiumdichloride

In a 50 ml Schlenk flask equipped with a magnetic stirrer chip andthree-way cock thoroughly purged with nitrogen, 0.571 g of (3-tert-butyl-cyclopentadienyl)(fluorenyl)diphenyl methane (1.26 mmol) was dissolvedin 20 ml of dehydrated diethyl ether in a nitrogen atmosphere. To thesolution, 1.85 ml of a n-butyl lithium/hexane solution (1.57 M: 2.90mmol) was gradually added dropwise in an ice bath and stirred at roomtemperature over night. The reaction solution was sufficiently cooled ina dry ice/methanol bath, and then 0.528 g of a complex of zirconiumtetrachloride and tetrahydrofuran (1:2) (1.40 mmol) was added to thesolution. The mixed solution was stirred for 2 days while graduallyreturning the temperature to room temperature and thereafter the solventwas distilled off under reduced pressure. The reaction mixture wasintroduced into a glove box, and thereafter re-slurried with dehydrateddiethyl ether and filtered with a glass filter filled with diatomaceousearth. The orange solid present on the filter was washed with a smallamount of dehydrated dichloromethane and the solvent was distilled offfrom the filtrate under reduced pressure, and thereby the aimed compoundwas obtained in an amount of 565 mg (0.922 mmol) as a red solid (yield:73%).

The identification was carried out by ¹H-NMR spectrum and FD-massspectrometry spectrum. The measurement results are shown below.

¹H-NMR spectrum (CDCl₃, TMS standard): /ppm 1.19 (s, 9H), 5.59 (t, 1H),5.76 (t, 1H), 6.22 (t, 1H), 6.35-6.42 (m, 2H), 6.94-7.03 (m, 2H),7.24-7.36 (m, 4H), 7.39-7.49 (m, 2H), 7.52-7.60 (m, 2H), 7.82-7.99 (m,4H), 8.15-8.20 (m, 2H) FD-mass spectrometry spectrum: M/z=612 (M⁺)

Example 5c Ethylene Polymerization

Into a 500 ml internal volume glass autoclave thoroughly purged withnitrogen, 250 ml of toluene was fed and ethylene was passed through at arate of 100 L/hr and then the autoclave was kept at 50° C. for 20 min ormore. Meanwhile, in a 30 ml side-arm flask thoroughly purged withnitrogen, a magnetic stirrer chip was put and then 0.5 μmol of a toluenesolution of diphenyl methylene(3-tert-butyl-5-methyl-cyclopentadienyl)(fluorenyl)zirconium dichloride synthesized in Example1c as a transition metal compound, and 0.5 mmol of a toluene solution ofmethyl aluminoxane (Al=1.53 M) were added and stirred for 30 min. Into aglass autoclave in which ethylene was passed through, 1.0 mmol of atoluene solution of triisobutyl aluminum (Al=1.0 M) was added and thenthe above solution was added, and polymerization was started. Thepolymerization was carried out at 50° C. at atmospheric pressure for 3min while ethylene was continuously passed through at a rate of 100L/hr, and a small amount of isopropanol was added to stop thepolymerization. The resulting polymer solution was added into excessamounts of methanol mixed with hydrochloric acid and the polymerprecipitated was separated with filtration. Thereafter, the polymer wasdried under reduced pressure at 80° C. for 10 hr. The polymer wasobtained in an amount of 0.58 g and had a polymerization activity of23.3 Kg-PE/mmol-Zr·hr. In the analysis results, the polymer had a [η]value of 10.5 dl/g, a Mw of 695,000 and a Mw/Mn ratio of 3.6.

Example 6c Ethylene Polymerization

Polymerization was carried out in the same conditions as Example 5cexcept for addingdiphenylmethylene(3-tert-butyl-5-methyl-cyclopentadienyl)(3,6-di-tert-butyl-fluorenyl)zirconiumdichloride synthesized in Example 2c as a transition metal compound. Thepolymer was obtained in an amount of 1.02 g and had a polymerizationactivity of 41.0 Kg-PE/mmol-Zr·hr. In the analysis results, the polymerhad a [η] value of 15.1 dl/g, a Mw of 1,066,000 and a Mw/Mn ratio of4.4.

Example 7c Ethylene Polymerization

Polymerization was carried out in the same conditions as Example 5cexcept for addingdiphenylmethylene(3-tert-butyl-5-methyl-cyclopentadienyl)(2,7-di-tert-butyl-fluorenyl)zirconiumdichloride synthesized in Example 3c as a transition metal compound. Thepolymer was obtained in an amount of 0.50 g and had a polymerizationactivity of 20.0 Kg-PE/mmol-Zr·hr. In the analysis results, the polymerhad a [η] value of 13.8 dl/g, a Mw of 1,068,000 and a Mw/Mn ratio of4.2.

Example 8c Ethylene Polymerization

Polymerization was carried out in the same conditions as Example 5cexcept thatdi(p-tolyl)methylene(3-tert-butyl-5-methyl-cyclopentadienyl)(fluorenyl)zirconiumdichloride synthesized in Example 4c was used as a transition metalcompound and the polymerization time was 2 min. The polymer was obtainedin an amount of 0.62 g and had a polymerization activity of 37.3Kg-PE/mmol-Zr·hr. In the analysis results, the polymer had a [η] valueof 10.4 dl/g, a Mw of 672,000 and a Mw/Mn ratio of 3.3.

Comparative Example 2c Ethylene Polymerization

Polymerization was carried out in the same conditions as Example 5cexcept for addingdimethylmethylene(3-tert-butyl-5-methyl-cyclopentadienyl)(fluorenyl)zirconiumdichloride synthesized by the method as described in the pamphlet ofWO01/27124, as a transition metal compound. The polymer was obtained inan amount of 1.97 g and had a polymerization activity of 79.7Kg-PE/mmol-Zr·hr. In the analysis results, the polymer had a [η] valueof 8.86 dl/g, a Mw of 635,000 and a Mw/Mn ratio of 3.4.

Comparative Example 3c Ethylene Polymerization

Polymerization was carried out in the same conditions as Example 5cexcept for addingdimethylmethylene(3-tert-butyl-5-methyl-cyclopentadienyl)(3,6-di-tert-butyl-fluorenyl)zirconiumdichloride synthesized by the method as described in WO01/27124, as atransition metal compound. The polymer was obtained in an amount of 1.69g and had a polymerization activity of 67.0 Kg-PE/mmol-Zr·hr. In theanalysis results, the polymer had a [η] value of 6.44 dl/g, a Mw of759,000 and a Mw/Mn ratio of 4.0.

Comparative Example 4c Ethylene polymerization

Polymerization was carried out in the same conditions as Example 5cexcept for addingdiphenylmethylene(3-tert-butyl-1-cyclopentadienyl)(fluorenyl)zirconiumdichloride synthesized in Comparative Example 1c, as a transition metalcompound. The polymer was obtained in an amount of 1.77 g and had apolymerization activity of 70.4 Kg-PE/mmol-Zr·hr. In the analysisresults, the polymer had a [η] value of 10.6 dl/g, a Mw of 994,000 and aMw/Mn ratio of 4.5.

Example 9c Propylene Polymerization

Into a 500 ml internal volume glass autoclave thoroughly purged withnitrogen, 250 ml of toluene was fed and propylene was passed through ata rate of 150 L/hr and then the autoclave was kept at 50° C. for 20 minor more. Meanwhile, in a 30 ml side-arm flask autoclave thoroughlypurged with nitrogen, a magnetic stirrer chip was put and then 5.0 μmolof a toluene solution of diphenylmethylene(3-tert-butyl-5-methyl-cyclopentadienyl)(fluorenyl)zirconiumdichloride synthesized in Example 1c as a transition metal compound, and5.0 mmol of a toluene solution of methyl aluminoxane (Al=1.53M) wereadded and stirred for 30 min. Into a glass autoclave in which propylenewas passed through, 1.0 mmol of a toluene solution of triisobutylaluminum (Al=1.0 M) was added and then the above solution was added, andpolymerization was started. The polymerization was carried out at 50° C.at atmospheric pressure for 30 min while propylene was continuouslypassed through at a rate of 150 L/hr, and a small amount of isopropanolwas added to stop the polymerization. The resulting polymer solution wasadded into excess amounts of methanol mixed with hydrochloric acid andthe polymer precipitated was separated with filtration. Thereafter, thepolymer was dried under reduced pressure at 80° C. for 10 hr. Thepolymer obtained was 9.46 g of isotactic polypropylene and had apolymerization activity of 3.78 Kg-PP/mmol-Zr·hr. In the analysisresults, the polymer had a Tm of 128.2° C., a [η] value of 1.05 dl/g, aMw of 108,000 and a Mw/Mn ratio of 1.8.

Example 10c Propylene Polymerization

Polymerization was carried out in the same conditions as Example 9cexcept for addingdiphenylmethylene(3-tert-butyl-5-methyl-cyclopentadienyl)(3,6-di-tert-butyl-fluorenyl)zirconiumdichloride synthesized in Example 2c as a transition metal compound. Thepolymer obtained was 1.30 g of isotactic polypropylene and had apolymerization activity of 0.52 Kg-PP/mmol-Zr·hr. In the analysisresults, the polymer had a Tm of 136.7° C., a [η] value of 0.89 dl/g, aMw of 88,000 and a Mw/Mn ratio of 1.7.

Example 11c Propylene Polymerization

Polymerization was carried out in the same conditions as Example 9cexcept for adding 4.1 μmol of a toluene solution ofdiphenylmethylene(3-tert-butyl-5-methyl-cyclopentadienyl)(2,7-di-tert-butyl-fluorenyl)zirconiumdichloride synthesized in Example 3c as a transition metal compound. Thepolymer obtained was 3.58 g of isotactic polypropylene and had apolymerization activity of 1.73 Kg-PP/mmol-Zr·hr. In the analysisresults, the polymer had a Tm of 133.8° C., a [η] value of 1.87 dl/g, aMw of 218,000 and a Mw/Mn ratio of 1.9.

Example 12c Propylene Polymerization

Polymerization was carried out in the same conditions as Example 9cexcept for addingdi(p-tolyl)methylene(3-tert-butyl-5-methyl-cyclopentadieny)(fluorenyl)zirconium dichloride synthesized in Example 4c as a transition metalcompound. The polymer obtained was 10.1 g of isotactic polypropylene andhad a polymerization activity of 3.99 Kg-PP/mmol-Zr·hr. In the analysisresults, the polymer had a Tm of 128.0° C., a [η] value of 1.02 dl/g, aMw of 94,000 and a Mw/Mn ratio of 1.8.

Comparative Example 5c Propylene Polymerization

Polymerization was carried out in the same conditions as Example 9cexcept for addingdimethylmethylene(3-tert-butyl-5-methyl-cyclopentadienyl)(fluorenyl)zirconiumdichloride synthesized by the method as described in WO01/27124, as atransition metal compound. The polymer obtained was 0.72 g of isotacticpolypropylene and had a polymerization activity of 0.28Kg-PP/mmol-Zr·hr. In the analysis results, the polymer had a Tm of133.6° C., a [η] value of 1.14 dl/g, a Mw of 77,000 and a Mw/Mn ratio of2.0.

Comparative Example 6c Propylene Polymerization

Polymerization was carried out in the same conditions as Example 9cexcept for addingdimethylmethylene(3-tert-butyl-5-methyl-cyclopentadienyl)(3,6-di-tert-butyl-fluorenyl)zirconiumdichloride synthesized by the method as described in WO01/27124, as atransition metal compound. The polymer obtained was 0.91 g of isotacticpolypropylene and had a polymerization activity of 0.37Kg-PP/mmol-Zr·hr. In the analysis results, the polymer had a Tm of142.4° C., a [η] value of 0.95 dl/g, a Mw of 95,000 and a Mw/Mn ratio of1.7.

Comparative Example 7c Propylene Polymerization

Polymerization was carried out in the same conditions as Example 9cexcept for addingdiphenylmethylene(3-tert-butyl-cyclopentadienyl)(fluorenyl)zirconiumdichloride synthesized in Comparative Example 1, as a transition metalcompound. The polymer obtained was 6.35 g of isotactic polypropylene andhad a polymerization activity of 2.55 Kg-PP/mmol-Zr·hr. In the analysisresults, the polymer had a Tm of 126.5° C., a [η] value of 0.33 dl/g, aMw of 26,000 and a Mw/Mn ratio of 1.6.

Example 13c Ethylene/Propylene Copolymerization

Into a 500 ml internal volume glass autoclave thoroughly purged withnitrogen, 250 ml of toluene was fed and ethylene and propylene werepassed through at a rate of 25 L/hr and 125 L/hr, respectively and thenthe autoclave was kept at 50° C. for 20 min or more. Meanwhile, in a 30ml side-arm flask autoclave thoroughly purged with nitrogen, a magneticstirrer chip was put and then 2.5 μmol of a toluene solution of diphenylmethylene(3-tert-butyl-5-methyl-cyclopentadienyl)(fluorenyl)zirconiumdichloride synthesized in Example 1c as a transition metal compound, and2.5 mmol of a toluene solution of methyl aluminoxane (Al=1.53M) wereadded and stirred for 30 min. Into a glass autoclave in which ethyleneand propylene were passed through, 1.0 mmol of a toluene solution oftriisobutyl aluminum (Al=1.0 M) was added and then the above solutionwas added, and polymerization was started. The polymerization wascarried out at 50° C. at atmospheric pressure for 20 min while ethyleneand propylene were continuously passed through at a rate of 25 L/hr and125 L/hr respectively, and a small amount of isopropanol was added tostop the polymerization. The resulting polymer solution was added intoexcess amounts of methanol mixed with hydrochloric acid and the polymerprecipitated was separated with filtration. Thereafter, the polymer wasdried under reduced pressure at 80° C. for 10 hr. The polymer wasobtained in an amount of 16.4 g and had a polymerization activity of19.8 Kg-Polymer/mmol-Zr·hr. In the analysis results, the polymer had anethylene content of 18 mol % and a [η] value of 1.20 dl/g.

Example 14c Ethylene/Propylene Copolymerization

Polymerization was carried out in the same conditions as Example 13cexcept for passing through ethylene at a rate of 50 L/hr and propyleneat a rate of 100 L/hr. The polymer was obtained in an amount of 19.9 gand had a polymerization activity of 23.6 Kg-Polymer/mmol-Zr·hr. In theanalysis results, the polymer had an ethylene content of 30 mol % and a[η] value of 1.23 dl/g.

Example 15c Ethylene/Propylene Copolymerization

Polymerization was carried out in the same conditions as Example 13cexcept that ethylene and propylene were passed through at a rate of 75L/hr and 75 L/hr, respectively and the polymerization time was 10 min.The polymer was obtained in an amount of 11.9 g and had a polymerizationactivity of 28.6 Kg-Polymer/mmol-Zr·hr. In the analysis results, thepolymer had an ethylene content of 46 mol % and a [η] value of 1.47dl/g.

Example 16c Ethylene/Propylene Copolymerization

Into a 500 ml internal volume glass autoclave thoroughly purged withnitrogen, 250 ml of toluene was fed and ethylene and propylene werepassed through at a rate of 25 L/hr and 125 L/hr, respectively and thenthe autoclave was kept at 50° C. for 20 min or more. Meanwhile, in a 30ml side-arm flask autoclave thoroughly purged with nitrogen, a magneticstirrer chip was put and then 2.5 μmol of a toluene solution of diphenylmethylene(3-tert-butyl-5-methyl-cyclopentadienyl)(3,6-di-tert-butyl-fluorenyl)zirconium dichloride synthesized in Example 2c, as atransition metal compound, and 2.5 mmol of a toluene solution of methylaluminoxane (Al=1.53M) were added and stirred for 30 min. Into a glassautoclave in which ethylene and propylene were passed through, 1.0 mmolof a toluene solution of triisobutyl aluminum (Al=1.0 M) was added andthen the above solution was added, and polymerization was started. Thepolymerization was carried out at 50° C. at atmospheric pressure for 20min while ethylene and propylene were continuously passed through at arate of 25 L/hr and 125 L/hr respectively, and a small amount ofisopropanol was added to stop the polymerization. The resulting polymersolution was added into excess amounts of methanol mixed withhydrochloric acid and the polymer precipitated was separated withfiltration. Thereafter, the polymer was dried under reduced pressure at80° C. for 10 hr. The polymer was obtained in an amount of 4.49 g andhad a polymerization activity of 5.40 Kg-Polymer/mmol-Zr·hr. In theanalysis results, the polymer had an ethylene content of 19 mol % and a[η] value of 0.88 dl/g.

Example 17c Ethylene/Propylene Copolymerization

Polymerization was carried out in the same conditions as Example 16cexcept for passing through ethylene at a rate of 50 L/hr and propyleneat a rate of 100 L/hr. The polymer was obtained in an amount of 6.98 gand had a polymerization activity of 8.39 Kg-Polymer/mmol-Zr·hr. In theanalysis results, the polymer had an ethylene content of 37 mol % and a[η] value of 0.94 dl/g.

Example 18c Ethylene/Propylene Copolymerization

Polymerization was carried out in the same conditions as Example 16cexcept that ethylene and propylene were passed through at a rate of 75L/hr and 75 L/hr, respectively. The polymer was obtained in an amount of8.89 g and had a polymerization activity of 10.7 Kg-Polymer/mmol-Zr·hr.In the analysis results, the polymer had an ethylene content of 46 mol %and a [η] value of 1.30 dl/g.

Example 19c Ethylene/Propylene Copolymerization

Into a 500 ml internal volume glass autoclave thoroughly purged withnitrogen, 250 ml of toluene was fed and ethylene and propylene werepassed through at a rate of 25 L/hr and 125 L/hr, respectively and thenthe autoclave was kept at 50° C. for more than 20 min. Meanwhile, in a30 ml side-arm flask thoroughly purged with nitrogen, a magnetic stirrerchip was put and then 2.5 μmol of a toluene solution of diphenylmethylene(3-tert-butyl-5-methyl-cyclopentadienyl)(2,7-di-tert-butyl-fluorenyl)zirconiumdichloride synthesized in Example 3c as a transition metal compound, and2.5 mmol of a toluene solution of methyl aluminoxane (Al=1.53M) wereadded and stirred for 30 min. Into a glass autoclave in which ethyleneand propylene were passed through, 1.0 mmol of a toluene solution oftriisobutyl aluminum (Al=1.0 M) was added and then the above solutionwas added, and polymerization was started. The polymerization wascarried out at 50° C. at atmospheric pressure for 10 min while ethyleneand propylene were continuously passed through at a rate of 25 L/hr and125 L/hr respectively, and a small amount of isopropanol was added tostop the polymerization. The resulting polymer solution was added intoexcess amounts of methanol mixed with hydrochloric acid and the polymerprecipitated was separated with filtration. Thereafter, the polymer wasdried under reduced pressure at 80° C. for 10 hr. The polymer wasobtained in an amount of 7.60 g and had a polymerization activity of18.3 Kg-Polymer/mmol-Zr·hr. In the analysis results, the polymer had anethylene content of 14 mol % and a [η] value of 1.59 dl/g.

Example 20c Ethylene/Propylene Copolymerization

Polymerization was carried out in the same conditions as Example 19cexcept for passing through ethylene at a rate of 50 L/hr and propyleneat a rate of 100 L/hr. The polymer was obtained in an amount of 9.53 gand had a polymerization activity of 22.9 Kg-Polymer/mmol-Zr·hr. In theanalysis results, the polymer had an ethylene content of 30 mol % and a[η] value of 1.55 dl/g.

Example 21c Ethylene/Propylene Copolymerization

Polymerization was carried out in the same conditions as Example 19cexcept that ethylene and propylene were passed through at a rate of 75L/hr and 75 L/hr, respectively, and the polymerization time was 8 min.The polymer was obtained in an amount of 7.94 g and had a polymerizationactivity of 23.8 Kg-Polymer/mmol-Zr·hr. In the analysis results, thepolymer had an ethylene content of 39 mol % and a [η] value of 1.65dl/g.

Example 22c Ethylene/Propylene Copolymerization

Into a 500 ml internal volume glass autoclave thoroughly purged withnitrogen, 250 ml of toluene was fed and ethylene and propylene werepassed through at a rate of 25 L/hr and 125 L/hr, respectively and thenthe autoclave was kept at 50° C. for 20 min or more. Meanwhile, in a 30ml side-arm flask thoroughly purged with nitrogen, a magnetic stirrerchip was put and then 2.5 μmol of a toluene solution ofdi(p-tolyl)methylene(3-tert-butyl-5-methyl-cyclopentadienyl)(fluorenyl)zirconiumdichloride synthesized in Example 4c as a transition metal compound, and2.5 mmol of a toluene solution of methyl aluminoxane (Al=1.53M) wereadded and stirred for 30 min. Into a glass autoclave in which ethyleneand propylene were passed through, 1.0 mmol of a toluene solution oftriisobutyl aluminum (Al=1.0 M) was added and then the above solutionwas added, and polymerization was started. The polymerization wascarried out at 50° C. at atmospheric pressure for 10 min while ethyleneand propylene were continuously passed through at a rate of 25 L/hr and125 L/hr respectively, and a small amount of isopropanol was added tostop the polymerization. The resulting polymer solution was added intoexcess amounts of methanol mixed with hydrochloric acid and the polymerprecipitated was separated with filtration. Thereafter, the polymer wasdried under reduced pressure at 80° C. for 10 hr. The polymer wasobtained in an amount of 9.52 g and had a polymerization activity of22.9 Kg-Polymer/mmol-Zr·hr. In the analysis results, the polymer had anethylene content of 19 mol % and a [η] value of 0.97 dl/g.

Example 23c Ethylene/Propylene Copolymerization

Polymerization was carried out in the same conditions as Example 22cexcept for passing through ethylene at a rate of 50 L/hr and propyleneat a rate of 100 L/hr. The polymer was obtained in an amount of 12.0 gand had a polymerization activity of 28.8 Kg-Polymer/mmol-Zr·hr. In theanalysis results, the polymer had an ethylene content of 32 mol % and a[η] value of 1.17 dl/g.

Example 24c Ethylene/Propylene Copolymerization

Polymerization was carried out in the same conditions as Example 22cexcept that ethylene and propylene were passed through at a rate of 75L/hr and 75 L/hr, respectively, and the polymerization time was 5 min.The polymer was obtained in an amount of 8.82 g and had a polymerizationactivity of 42.4 Kg-Polymer/mmol-Zr·hr. In the analysis results, thepolymer had an ethylene content of 43 mol % and a [η] value of 1.29dl/g.

Comparative Example 8c Ethylene/Propylene Copolymerization

Into a 500 ml internal volume glass autoclave thoroughly purged withnitrogen, 250 ml of toluene was fed and ethylene and propylene werepassed through at a rate of 25 L/hr and 125 L/hr, respectively and thenthe autoclave was kept at 50° C. for 20 min or more. Meanwhile, in a 30ml side-arm flask thoroughly purged with nitrogen, a magnetic stirrerchip was put and then 2.5 μmol of a toluene solution of dimethylmethylene(3-tert-butyl-5-methyl-cyclopentadienyl)(fluorenyl)zirconiumdichloride synthesized by the method disclosed in WO01/27124, as atransition metal compound, and 2.5 mmol of a toluene solution of methylaluminoxane (Al=1.53M) were added and stirred for 30 min. Into a glassautoclave in which ethylene and propylene were passed through, 1.0 mmolof a toluene solution of triisobutyl aluminum (Al=1.0 M) was added andthen the above solution was added, and polymerization was started. Thepolymerization was carried out at 50° C. at atmospheric pressure for 20min while ethylene and propylene were continuously passed through at arate of 25 L/hr and 125 L/hr respectively, and a small amount ofisopropanol was added to stop the polymerization. The resulting polymersolution was added into excess amounts of methanol mixed withhydrochloric acid and the polymer precipitated was separated withfiltration. Thereafter, the polymer was dried under reduced pressure at80° C. for 10 hr. The polymer was obtained in an amount of 1.97 g andhad a polymerization activity of 2.35 Kg-Polymer/mmol-Zr·hr. In theanalysis results, the polymer had an ethylene content of 31 mol % and a[η] value of 0.83 dl/g.

Comparative Example 9c Ethylene/Propylene Copolymerization

Polymerization was carried out in the same conditions as ComparativeExample 8c except for passing through ethylene at a rate of 50 L/hr andpropylene at a rate of 100 L/hr. The polymer was obtained in an amountof 2.52 g and had a polymerization activity of 3.03Kg-Polymer/mmol-Zr·hr. In the analysis results, the polymer had anethylene content of 44 mol % and a [η] value of 1.00 dl/g.

Comparative Example 10c Ethylene/Propylene Copolymerization

Polymerization was carried out in the same conditions as ComparativeExample 8c except for passing through ethylene at a rate of 75 L/hr andpropylene at a rate of 75 L/hr. The polymer was obtained in an amount of3.29 g and had a polymerization activity of 3.95 Kg-Polymer/mmol-Zr·hr.In the analysis results, the polymer had an ethylene content of 59 mol %and a [η] value of 1.30 dl/g.

Comparative Example 11c Ethylene/Propylene Copolymerization

Into a 500 ml internal volume glass autoclave thoroughly purged withnitrogen, 250 ml of toluene was fed and ethylene and propylene werepassed through at a rate of 25 L/hr and 125 L/hr, respectively and thenthe autoclave was kept at 50° C. for 20 min or more. Meanwhile, in a 30ml side-arm flask thoroughly purged with nitrogen, a magnetic stirrerchip was put and then 2.5 μmol of a toluene solution of dimethylmethylene(3-tert-butyl-5-methyl-cyclopentadienyl)(3,6-di-tert-butyl-fluorenyl)zirconiumdichloride synthesized by the method disclosed in the pamphlet ofWO01/27124, as a transition metal compound, and 2.5 mmol of a toluenesolution of methyl aluminoxane (Al=1.53M) were added and stirred for 30min. Into a glass autoclave in which ethylene and propylene were passedthrough, 1.0 mmol of a toluene solution of triisobutyl aluminum (Al=1.0M) was added and then the above solution was added, and polymerizationwas started. The polymerization was carried out at 50° C. at atmosphericpressure for 20 min while ethylene and propylene were continuouslypassed through at a rate of 25 L/hr and 125 L/hr respectively, and asmall amount of isopropanol was added to stop the polymerization. Theresulting polymer solution was added into excess amounts of methanolmixed with hydrochloric acid and the polymer precipitated was separatedwith filtration. Thereafter, the polymer was dried under reducedpressure at 80° C. for 10 hr. The polymer was obtained in an amount of0.34 g and had a polymerization activity of 0.40 Kg-Polymer/mmol-Zr·hr.In the analysis results, the polymer had an ethylene content of 29 mol %and a [η] value of 0.58 dl/g.

Comparative Example 12c Ethylene/Propylene Copolymerization

Polymerization was carried out in the same conditions as ComparativeExample 11c except for passing through ethylene at a rate of 50 L/hr andpropylene at a rate of 100 L/hr. The polymer was obtained in an amountof 1.22 g and had a polymerization activity of 1.49Kg-Polymer/mmol-Zr·hr. In the analysis results, the polymer had anethylene content of 45 mol % and a [η] value of 0.78 dl/g.

Comparative Example 13c Ethylene/Propylene Copolymerization

Polymerization was carried out in the same conditions as ComparativeExample 11c except for passing through ethylene at a rate of 75 L/hr andpropylene at a rate of 75 L/hr. The polymer was obtained in an amount of2.19 g and had a polymerization activity of 2.63 Kg-Polymer/mmol-Zr·hr.In the analysis results, the polymer had an ethylene content of 63 mol %and a [η] value of 1.18 dl/g.

Comparative Example 14c Ethylene/Propylene Copolymerization

Into a 500 ml internal volume glass autoclave thoroughly purged withnitrogen, 250 ml of toluene was fed and ethylene and propylene werepassed through at a rate of 25 L/hr and 125 L/hr, respectively and thenthe autoclave was kept at 50° C. for 20 min or more. Meanwhile, in a 30ml side-arm flask thoroughly purged with nitrogen, a magnetic stirrerchip was put and then 2.5 μmol of a toluene solution of diphenylmethylene(3-tert-butyl-cyclopentadienyl)(fluorenyl)zirconium dichloridesynthesized in Comparative Example 1c as a transition metal compound,and 2.5 mmol of a toluene solution of methyl aluminoxane (Al=1.53M) wereadded and stirred for 30 min. Into a glass autoclave in which ethyleneand propylene were passed through, 1.0 mmol of a toluene solution oftriisobutyl aluminum (Al=1.0 M) was added and then the above solutionwas added, and polymerization was started. The polymerization wascarried out at 50° C. at atmospheric pressure for 10 min while ethyleneand propylene were continuously passed through at a rate of 25 L/hr and125 L/hr respectively, and a small amount of isopropanol was added tostop the polymerization. The resulting polymer solution was added intoexcess amounts of methanol mixed with hydrochloric acid and the polymerprecipitated was separated with filtration. Thereafter, the polymer wasdried under reduced pressure at 80° C. for 10 hr. The polymer wasobtained in an amount of 12.4 g and had a polymerization activity of29.7 Kg-Polymer/mmol-Zr·hr. In the analysis results, the polymer had anethylene content of 21 mol % and a [η] value of 0.46 dl/g.

Comparative Example 15c Ethylene/Propylene Copolymerization

Polymerization was carried out in the same conditions as ComparativeExample 14c except for passing through ethylene at a rate of 50 L/hr andpropylene at a rate of 100 L/hr. The polymer was obtained in an amountof 13.5 g and had a polymerization activity of 32.4Kg-Polymer/mmol-Zr·hr. In the analysis results, the polymer had anethylene content of 35 mol % and a [η] value of 0.78 dl/g.

Comparative Example 16c Ethylene/Propylene Copolymerization

Polymerization was carried out in the same conditions as ComparativeExample 14c except for passing ethylene at a rate of 75 L/hr andpropylene at a rate of 75 L/hr. The polymer was obtained in an amount of15.9 g and had a polymerization activity of 38.2 Kg-Polymer/mmol-Zr·hr.In the analysis results, the polymer had an ethylene content of 48 mol %and a [η] value of 0.72 dl/g.

The polymerization results are inclusively shown in Tables 1c and 2c.

TABLE 1c Transition metal compound MAO Polymerization Polymerization Zrconcentration Al concenTration time Yield activity Ex. Kind [μmol][mmol] [min] [g] [Kg/mmol-Zr · h]  9c A 5 5 30 9.46 3.78 13c A 2.5 2.520 16.4 19.8 14c A 2.5 2.5 20 19.9 23.6 15c A 2.5 2.5 10 11.9 28.6  5c A0.5 0.5 3 0.58 23.3 10c B 5 5 30 1.3 0.52 16c B 2.5 2.5 20 4.49 5.4 17cB 2.5 2.5 20 6.98 8.39 18c B 2.5 2.5 20 8.89 10.7  6c B 0.5 0.5 3 1.0241 11c C 4.1 5 30 3.58 1.73 19c C 2.5 2.5 10 7.6 18.3 20c C 2.5 2.5 109.53 22.9 21c C 2.5 2.5 8 7.94 23.8  7c C 0.5 0.5 3 0.5 20 12c D 5 5 3010.1 3.99 22c D 2.5 2.5 10 9.52 22.9 23c D 2.5 2.5 10 12 28.8 24c D 2.52.5 5 8.82 42.4  8c D 0.5 0.5 2 0.62 37.3 Ethylene content in polymer[η] Mw Mw/Mn Tm Ex. [mol %] [dl/g] [×10³] [—] [° C.]  9c 0 1.05 108 1.8128.2 13c 18 1.2 — — — 14c 30 1.23 — — — 15c 46 1.47 — — —  5c 100 10.5696 3.6 — 10c 0 0.89  88 1.7 136.7 16c 19 0.88 — — — 17c 37 0.94 — — —18c 46 1.3 — — —  6c 100 15.1 1066  4.4 — 11c 0 1.87 218 1.9 133.8 19c14 1.59 — — — 20c 30 1.55 — — — 21c 39 1.65 — — —  7c 100 13.8 1068  4.2— 12c 0 1.02  94 1.8 128   22c 19 0.97 — — — 23c 32 1.17 — — — 24c 431.29 — — —  8c 100 10.4 672 3.3 — Polymerization conditions: Toluene;250 ml, Temperature; 50° C., Triisobutyl aluminum; 1.0 mmol, Amount ofMonomer fed; refer to each example. Transition metal compound A:Diphenylmethylene(3-tert-butyl-5-methyl-cyclopentadienyl)(fluorenyl)zirconiumdichloride Transition metal compound B:Diphenylmethylene(3-tert-butyl-5-methyl-cyclopentadienyl)(3,6-di-tert-butyl-fluorenyl)zirconiumdichloride Transition metal compound C:Diphenylmethylene(3-tert-butyl-5-methyl-cyclopentadienyl)(2,7-di-tert-butyl-fluorenyl)zirconiumdichloride Transition metal compound D:Di(p-tolyl)methylene(3-tert-butyl-5-methyl-cyclopentadienyl)(fluorenyl)zirconiumdichloride

TABLE 2c Transition metal MAO compound Al Polymerization PolymerizationComparative Zr concentration concentration time Yield activity ExampleKind [μmol] [mmol] [min] [g] [Kg/mmol-Zr · h] 5c E 5 5 30 0.72 0.28 8c E2.5 2.5 20 1.97 2.35 9c E 2.5 2.5 20 2.52 3.03 10c  E 2.5 2.5 20 3.293.95 2c E 0.5 0.5 3 1.97 79.7 6c F 5 5 30 0.91 0.37 11c  F 2.5 2.5 200.34 0.4 12c  F 2.5 2.5 20 1.22 1.49 13c  F 2.5 2.5 20 2.19 2.63 3c F0.5 0.5 3 1.69 67 7c G 5 5 30 6.35 2.55 14c  G 2.5 2.5 10 12.4 29.7 15c G 2.5 2.5 10 13.5 32.4 16c  G 2.5 2.5 10 15.9 38.2 4c G 0.5 0.5 3 1.7770.4 Ethylene content in Comparative polymer [η] Mw Mw/Mn Tm Example[mol %] [dl/g] [×10³] [—] [° C.] 5c 0 1.14  77 2   133.6 8c 31 0.83 — —— 9c 44 1.00 — — — 10c  59 1.30 — — — 2c 100 8.86 635 3.4 — 6c 0 0.95 95 1.7 142.4 11c  29 0.58 — — — 12c  45 0.78 — — — 13c  63 1.18 — — —3c 100 6.44 759 4.0 — 7c 0 0.33  26 1.6 126.5 14c  21 0.46 — — — 15c  350.78 — — — 16c  48 0.72 — — — 4c 100 10.6 994 4.5 — Polymerizationconditions: Toluene 250 ml, Temperature 50° C., Triisobutyl aluminum 1.0mmol, Amount of Monomer fed shown in each example. Transition metalcompound E:Dimethylmethylene(3-tert-butyl-5-methyl-cyclopentadienyl)(fluorenyl)zirconiumdichloride Transition metal compound F:Dimethylmethylene(3-tert-butyl-5-methyl-cyclopentadienyl)(3,6-di-tert-butyl-fluorenyl)zirconiumdichloride Transition metal compound G:Diphenylmethylene(3-tert-butyl-cyclopentadienyl)(fluorenyl)zirconiumdichloride

Example 25c Ethylene/Propylene Pressure Solution Copolymerization

Into a 1000 ml internal volume SUS-made autoclave thoroughly purged withnitrogen, 425 ml of heptane was fed, and then 27.5 ml of propylene wasfed while sufficiently stirring. The mixture was heated to 60° C. andthe internal pressure of the autoclave was set to 5.7 Kg/cm²G, and thenset to 8.0 Kg/cm²G by pressurization with ethylene gas. Successively, toa 20 ml internal volume catalyst feed pot mounted on the autoclave,which pot was thoroughly purged with nitrogen, a mixed solution of 2.0ml of dehydrated toluene and 0.5 mmol of a toluene solution oftriisobutyl aluminum (Al=1.0 M) was added and fed into the autoclave bypressurization with nitrogen. Next, to the catalyst feed pot, 2.0 ml ofdehydrated toluene, 0.2 mmol of a toluene solution of methyl aluminoxane(Al=1.53 M) and 0.2 μmol of a toluene solution of diphenylmethylene(3-tert-butyl-5-methyl-cyclopentadienyl)(fluorenyl)zirconiumdichloride synthesized in Example 1c, as a transition metal compoundwere added, and fed by pressurization with nitrogen, and thenpolymerization was started. The polymerization was carried out at 60° C.for 15 min while the internal pressure of the autoclave was kept to 8.0Kg/cm²G, and then a small amount of methanol was added to stop thepolymerization. The resulting polymer solution was added into excessamounts of methanol mixed with hydrochloric acid and the polymerprecipitated was separated with filtration. Thereafter, the polymer wasdried under reduced pressure at 80° C. for 10 hr. The polymer wasobtained in an amount of 10.6 g and had a polymerization activity of 212Kg-Polymer/mmol-Zr·hr. In the analysis results, the polymer had anethylene content of 37 mol %, a [η] value of 2.44 dl/g, a Mw of 382,000and a Mw/Mn ratio of 2.0.

Example 26c Ethylene/Propylene Pressure Solution Copolymerization

Polymerization was carried out in the same conditions as Example 25cexcept for adding 0.5 mmol of a toluene solution of methyl aluminoxane(Al=1.53 M) and 0.5 μmol of a toluene solution ofdiphenylmethylene(3-tert-butyl-5-methyl-cyclopentadienyl)(3,6-di-tert-butyl-fluorenyl)zirconiumdichloride synthesized in Example 2c, as a transition metal compound.The polymer was obtained in an amount of 11.4 g and had a polymerizationactivity of 91.1 Kg-Polymer/mmol-Zr·hr. In the analysis results, thepolymer had an ethylene content of 39 mol % and a [η] value of 1.78dl/g, a Mw of 228,000 and a Mw/Mn ratio of 1.9.

Comparative Example 17c Ethylene/Propylene Pressure SolutionCopolymerization

Polymerization was carried out in the same conditions as Example 25cexcept for adding 0.5 mmol of a toluene solution of methyl aluminoxane(Al=1.53 M) and 0.5 μmol of a toluene solution ofdimethylmethylene(3-tert-butyl-5-methyl-cyclopentadienyl)(fluorenyl)zirconium dichloride synthesized by themethod disclosed in the pamphlet of WO01/27124, as a transition metalcompound. The polymer was obtained in an amount of 8.74 g and had apolymerization activity of 69.9 Kg-Polymer/mmol-Zr·hr. In the analysisresults, the polymer had an ethylene content of 45 mol % and a [η] valueof 1.24 dl/g, a Mw of 149,000 and a Mw/Mn ratio of 1.8.

Comparative Example 18c Ethylene/Propylene Pressure SolutionCopolymerization

Polymerization was carried out in the same conditions as Example 25cexcept for adding 0.5 mmol of a toluene solution of methyl aluminoxane(Al=1.53 M) and 0.5 μmol of a toluene solution ofdimethylmethylene(3-tert-butyl-5-methyl-cyclopentadienyl)(3,6-di-tert-butyl-fluorenyl)zirconiumdichloride synthesized by the method disclosed in the pamphlet ofWO01/27124, as a transition metal compound. The polymer was obtained inan amount of 10.8 g and had a polymerization activity of 86.6Kg-Polymer/mmol-Zr·hr. In the analysis results, the polymer had anethylene content of 43 mol % and a [η] value of 1.06 dl/g, a Mw of124,000 and a Mw/Mn ratio of 1.8.

The polymerization results are inclusively shown in Table 3c.

TABLE 3c Transition metal MAO compound Al Polymerization PolymerizationZr concentration concentration time Yield activity Kind [μmol] [mmol][min] [g] [Kg/mmol-Zr · h] Example 25c A 0.2 0.2 15 10.6 212 26c B 0.50.5 15 11.4 91.1 Comparative Example 17c E 0.5 0.5 15 8.74 69.9 18c F0.5 0.5 15 10.8 86.6 Ethylene content in polymer [η] Mw Mw/Mn [mol %][dl/g] [×10³] [—] Example 25c 37 2.44 382 2.0 26c 39 1.78 228 1.9Comparative Example 17c 45 1.24 149 1.8 18c 43 1.06 124 1.8Polymerization conditions: Heptane 425 ml, Propylene 27.5 ml,Temperature 60° C., Pressure 8.0 Kg/cm²G, Triisobutyl aluminum 0.5 mmol.Transition metal compound A:Diphenylmethylene(3-tert-butyl-5-methyl-cyclopentadienyl)(fluorenyl)zirconiumdichloride Transition metal compound B:Diphenylmethylene(3-tert-butyl-5-methyl-cyclopentadienyl)(3,6-di-tert-butyl-fluorenyl)zirconiumdichloride Transition metal compound E:Dimethylmethylene(3-tert-butyl-5-methyl-cyclopentadienyl)(fluorenyl)zirconiumdichloride Transition metal compound F:Dimethylmethylene(3-tert-butyl-5-methyl-cyclopentadienyl)(3,6-di-tert-butyl-fluorenyl)zirconiumdichloride

Example 27c Propylene Bulk Polymerization

Into a 50 ml side-arm flask thoroughly purged with nitrogen, a magneticstirrer chip was put and then 0.24 mmol in terms of aluminum of amineral oil suspension of silica-supported methyl aluminoxane (Al=7.10mmol/g) and 1.08 μmol of a toluene solution of diphenylmethylene(3-tert-butyl-5-methyl-cyclopentadienyl)(fluorenyl)zirconiumdichloride synthesized in Example 1c as a transition metal compound wereadded and stirred for 30 min. To the mixed solution, 1.0 mmol of ahexane solution of triisobutyl aluminum (Al=1.0 M) and 5.0 ml ofdehydrated hexane were added and then introduced into a 2000 ml internalvolume SUS-made autoclave thoroughly purged with nitrogen. Thereafter,500 g of liquid propylene was fed and polymerization was carried out at70° C. for 40 min, and then the autoclave was cooled and propylene waspurged to stop the polymerization. The resulting polymer was dried underreduced pressure at 80° C. for 10 hr. The polymer obtained was 16.0 g ofisotactic polypropylene and had a polymerization activity of 22.1Kg-PP/mmol-Zr·hr. In the analysis results, the polymer had a [η] valueof 3.55 dl/g, a Mw of 622,000 and a Mw/Mn ratio of 3.9 and a Tm of137.4° C.

Example 28c Propylene Bulk Polymerization

Polymerization was carried out in the same conditions as Example 27cexcept that 0.30 Nl of hydrogen was added after 500 g of the liquidpropylene was fed. The polymer obtained was 67.4 g of isotacticpolypropylene and had a polymerization activity of 93. Kg-PP/mmol-Zr·hr.In the analysis results, the polymer had a [η] value of 1.61 dl/g, a Mwof 198,000 and a Mw/Mn ratio of 2.4 and a Tm of 142.7° C.

Example 29c Propylene Bulk Polymerization

Into a 50 ml side-arm flask thoroughly purged with nitrogen, a magneticstirrer chip was put and then 0.54 mmol in terms of aluminum of amineral oil suspension of silica-supported methyl aluminoxane (Al=7.92mmol/g) and 0.92 μmol of a toluene solution of diphenylmethylene(3-tert-butyl-5-methyl-cyclopentadienyl)(3,6-di-tert-butyl-fluorenyl)zirconiumdichloride synthesized in Example 2c as a transition metal compound wereadded and stirred for 30 min. To the mixed solution, 1.0 mmol of ahexane solution of triisobutyl aluminum (Al=1.0 M) and 5.0 ml ofdehydrated hexane were added and then introduced into a 2000 ml internalvolume SUS-made autoclave thoroughly purged with nitrogen. Thereafter,500 g of liquid propylene was fed and polymerization was carried out at70° C. for 40 min, and then the autoclave was cooled and propylene waspurged to stop the polymerization. The resulting polymer was dried underreduced pressure at 80° C. for 10 hr. The polymer obtained was 6.30 g ofisotactic polypropylene and had a polymerization activity of 10.3Kg-PP/mmol-Zr·hr. In the analysis results, the polymer had a [η] valueof 2.58 dl/g, a Mw of 442,000 and a Mw/Mn ratio of 2.5 and a Tm of144.8° C.

Example 30c Propylene Bulk Polymerization

Polymerization was carried out in the same conditions as Example 29cexcept that 0.30 Nl of hydrogen was added after 500 g of the liquidpropylene was fed. The polymer obtained was 99.8 g of isotacticpolypropylene and had a polymerization activity of 163 Kg-PP/mmol-Zr·hr.In the analysis results, the polymer had a [η] value of 1.02 dl/g, a Mwof 107,000 and a Mw/Mn ratio of 2.2 and a Tm of 155. ° C.

Comparative Example 19c Propylene Bulk Polymerization

Into a 50 ml side-arm flask thoroughly purged with nitrogen, a magneticstirrer chip was put and then 0.24 mmol in terms of aluminum of amineral oil suspension of silica-supported methyl aluminoxane (Al=7.10mmol/g) and 1.35 μmol of a toluene solution of dimethylmethylene(3-tert-butyl-5-methyl -cyclopentadienyl)(fluorenyl)zirconiumdichloride synthesized by the method disclosed in the pamphlet ofWO01/27124 as a transition metal compound were added and stirred for 30min. To the mixed solution, 1.0 mmol of a hexane solution of triisobutylaluminum (Al=1.0 M) and 5.0 ml of dehydrated hexane were added and thenintroduced into a 2000 ml internal volume SUS-made autoclave thoroughlypurged with nitrogen. Thereafter, 500 g of liquid propylene was fed andpolymerization was carried out at 70° C. for 40 min, and then theautoclave was cooled and propylene was purged to stop thepolymerization. The resulting polymer was dried under reduced pressureat 80° C. for 10 hr. The polymer obtained was 39.9 g of isotacticpolypropylene and had a polymerization activity of 44.2Kg-PP/mmol-Zr·hr. In the analysis results, the polymer had a [η] valueof 3.19 dl/g, a Mw of 489,000 and a Mw/Mn ratio of 2.6 and a Tm of140.9° C.

Comparative Example 20c Propylene Bulk Polymerization

Polymerization was carried out in the same conditions as ComparativeExample 19c except that 0.30 Nl of hydrogen was added after 500 g of theliquid propylene was fed. The polymer obtained was 101 g of isotacticpolypropylene and had a polymerization activity of 112 Kg-PP/mmol-Zr·hr.In the analysis results, the polymer had a [η] value of 1.85 dl/g, a Mwof 229,000 and a Mw/Mn ratio of 2.4 and a Tm of 143.6° C.

Comparative Example 21c Propylene Bulk Polymerization

Into a 50 ml side-arm flask thoroughly purged with nitrogen, a magneticstirrer chip was put and then 0.54 mmol in terms of aluminum of amineral oil suspension of silica-supported methyl aluminoxane (Al=7.9mmol/g) and 1.11 μmol of a toluene solution of dimethylmethylene(3-tert-butyl-5-methyl-cyclopentadienyl)(3,6-di-tert-butyl-fluorenyl)zirconiumdichloride synthesized by the method disclosed in the pamphlet ofWO01/27124, as a transition metal compound were added and stirred for 30min. To the mixed solution, 1.0 mmol of a hexane solution of triisobutylaluminum (Al=1.0 M) and 5.0 ml of dehydrated hexane were added and thenintroduced into a 2000 ml internal volume SUS-made autoclave thoroughlypurged with nitrogen. Thereafter, 500 g of liquid propylene was fed andpolymerization was carried out at 70° C. for 40 min, and then theautoclave was cooled and propylene was purged to stop thepolymerization. The resulting polymer was dried under reduced pressureat 80° C. for 10 hr. The polymer obtained was 8.23 g of isotacticpolypropylene and had a polymerization activity of 11.2Kg-PP/mmol-Zr·hr. In the analysis results, the polymer had a [η] valueof 3.35 dl/g, a Mw of 437,000 and a Mw/Mn ratio of 2.4 and a Tm of149.4° C.

Comparative Example 22c Propylene Bulk Polymerization

Polymerization was carried out in the same conditions as ComparativeExample 21c except that 0.30 Nl of hydrogen was added after 500 g of theliquid propylene was fed. The polymer obtained was 108 g of isotacticpolypropylene and had a polymerization activity of 146 Kg-PP/mmol-Zr·hr.In the analysis results, the polymer had a [η] value of 1.60 dl/g, a Mwof 178,000 and a Mw/Mn ratio of 2.2 and a Tm of 158.2° C.

Comparative Example 23c Propylene Bulk Polymerization

Into a 50 ml side-arm flask thoroughly purged with nitrogen, a magneticstirrer chip was put and then 0.24 mmol in terms of aluminum of amineral oil suspension of silica-supported methyl aluminoxane (Al=7.10mmol/g) and 1.11 μmol of a toluene solution ofdiphenylmethylene(3-tert-butyl-cyclopentadienyl)(fluorenyl)zirconiumdichloride synthesized in Comparative Example 1C, as a transition metalcompound were added and stirred for 30 min. To the mixed solution, 1.0mmol of a hexane solution of triisobutyl aluminum (Al=1.0 M) and 5.0 mlof dehydrated hexane were added and then introduced into a 2000 mlinternal volume SUS-made autoclave thoroughly purged with nitrogen.Thereafter, 500 g of liquid propylene was fed and polymerization wascarried out at 70° C. for 40 min, and then the autoclave was cooled andpropylene was purged to stop the polymerization. The resulting polymerwas dried under reduced pressure at 80° C. for 10 hr. The polymerobtained was 39.5 g of isotactic polypropylene and had a polymerizationactivity of 53.4 Kg-PP/mmol-Zr·hr. In the analysis results, the polymerhad a [η] value of 1.02 dl/g, a Mw of 103,000 and a Mw/Mn ratio of 1.9and a Tm of 130.6° C.

Comparative Example 24c Propylene Bulk Polymerization

Polymerization was carried out in the same conditions as ComparativeExample 23c except that 0.30 Nl of hydrogen was added after 500 g of theliquid propylene was fed. The polymer obtained was 143 g of isotacticpolypropylene and had a polymerization activity of 193 Kg-PP/mmol-Zr·hr.In the analysis results, the polymer had a [η] value of 0.53 dl/g, a Mwof 41,000 and a Mw/Mn ratio of 1.7 and a Tm of 133.8° C.

The polymerization results are inclusively shown in Table 4c.

TABLE 4c Transition metal compound MAO Polymerization Zr concentrationAl concentration Hydrogen time Yield Kind [μmol] [mmol] [Nl] [min] [g]Example 27c A 1.08 0.24 — 40 16 28c A 1.08 0.24 0.3 40 67.4 29c B 0.920.54 — 40 6.3 30c B 0.92 0.54 0.3 40 99.8 Comparative Example 19c E 1.350.24 — 40 39.9 20c E 1.35 0.24 0.3 40 101 21c F 1.11 0.54 — 40 8.23 22cF 1.11 0.54 0.3 40 108 23c G 1.11 0.24 — 40 39.5 24c G 1.11 0.24 0.3 40143 Polymerization activity [η] Mw Mw/Mn Tm [Kg/mmol-Zr · h] [dl/g][×10³] [—] [° C.] Example 27c 22.1 3.55 622 3.9 137.4 28c 93.2 1.61 1982.4 142.7 29c 10.3 2.58 442 2.5 144.8 30c 163 1.02 107 2.2 155.1Comparative Example 19c 44.2 3.19 489 2.6 140.9 20c 112 1.85 229 2.4143.6 21c 11.2 3.35 437 2.4 149.4 22c 146 1.6 178 2.2 158.2 23c 53.41.02 103 1.9 130.6 24c 193 0.53 41 1.7 133.8 Polymerization conditions:Liquid propylene 500 g, Temperature 70° C., Triisobutyl aluminum 1.0mmol. Transition metal compound A:Diphenylmethylene(3-tert-butyl-5-methyl-cyclopentadienyl)(fluorenyl)zirconiumdichloride Transition metal compound B:Diphenylmethylene(3-tert-butyl-5-methyl-cyclopentadienyl)(3,6-di-tert-butyl-fluorenyl)zirconiumdichloride Transition metal compound E:Dimethylmethylene(3-tert-butyl-5-methyl-cyclopentadienyl)(fluorenyl)zirconiumdichloride Transition metal compound F:Dimethylmethylene(3-tert-butyl-5-methyl-cyclopentadienyl)(3,6-di-tert-butyl-fluorenyl)zirconiumdichloride Transition metal compound G:Diphenylmethylene(3-tert-butyl-5-methyl-cyclopentadienyl)(fluorenyl)zirconiumdichloride

Example 31c Ethylene/Propylene Bulk Copolymerization

Into a 200 ml four-necked flask thoroughly purged with nitrogen, amagnetic stirrer chip was put and then 9.94 mmol in terms of aluminum ofa toluene suspension of silica-supported methyl aluminoxane (Al=7.10mmol/g) and 22.3 μmol of a toluene solution of diphenylmethylene(3-tert-butyl-5-methyl-cyclopentadienyl)(fluorenyl)zirconiumdichloride synthesized in Example 1c as a transition metal compound wereadded and stirred for 30 min. Thereafter, 99% of the solvent wasreplaced with normal heptane by decantation to prepare 40 ml of asuspension finally.

To a 50 ml side-arm flask thoroughly purged with nitrogen, a magneticstirrer chip was put, and 5.0 ml of the suspension and 0.84 mmol of anormal heptane solution of triethyl aluminum (Al=1.25 M) were added andstirred for 15 min. Subsequently, to a 5000 ml internal volume SUS-madeautoclave thoroughly purged with nitrogen, 1.92 μmol in terms oftransition metal compound of the suspension (0.85 mmol in terms ofaluminum of methyl aluminoxane) and 6.35 ml of a heptane solution ofEPAN720 (EPAN720=1.91 mg/ml) as an antifouling agent were introduced.Thereafter, 1500 g of liquid propylene and 5.0 Nl of ethylene were fedand polymerization was carried out at 60° C. for 60 min, and then theautoclave was cooled and propylene was purged to stop thepolymerization. The resulting polymer was dried under reduced pressureat 80° C. for 6 hr. The polymer was obtained in an amount of 133 g andhad a polymerization activity of 69.5 Kg-Polymer/mmol-Zr·hr. In theanalysis results, the polymer had an ethylene content of 2.6 mol %, a[η] value of 2.72 dl/g and a Tm of 129.7° C.

Example 32c Ethylene/Propylene Bulk Copolymerization

Polymerization was carried out in the same conditions as Example 31cexcept that 10 Nl of ethylene was added. The polymer was obtained in anamount of 288 g and had a polymerization activity of 150Kg-Polymer/mmol-Zr·hr. In the analysis results, the polymer had anethylene content of 4.4 mol %, a [η] value of 2.63 dl/g and a Tm of120.7° C.

Comparative Example 25c Ethylene/Propylene Bulk Copolymerization

Into a 200 ml four-necked flask thoroughly purged with nitrogen, amagnetic stirrer chip was put and then 9.94 mmol in terms of aluminum ofa toluene suspension of silica-supported methyl aluminoxane (Al=7.10mmol/g) and 27.9 μmol of a toluene solution of dimethylmethylene(3-tert-butyl-5-methyl -cyclopentadienyl)(fluorenyl)zirconiumdichloride synthesized by the method disclosed in the pamphlet ofWO01/27124 as a transition metal compound were added and stirred for 30min. Thereafter, 99% of the solvent was replaced with normal heptane bydecantation to prepare 40 ml of a suspension finally.

To a 50 ml side-arm flask thoroughly purged with nitrogen, a magneticstirrer chip was put, and 5.0 ml of the suspension and 1.04 mmol of anormal heptane solution of triethyl aluminum (Al=1.25 M) were added andstirred for 15 min. Subsequently, to a 5000 ml internal volume SUS-madeautoclave thoroughly purged with nitrogen, 1.79 μmol in terms oftransition metal compound of the suspension (0.64 mmol in terms ofaluminum of methyl aluminoxane) and 4.76 ml of a heptane solution ofEPAN720 (EPAN720=1.91 mg/ml) as an antifouling agent were introduced.Thereafter, 1500 g of liquid propylene and 10 Nl of ethylene were fedand polymerization was carried out at 60° C. for 60 min, and then theautoclave was cooled and propylene was purged to stop thepolymerization. The resulting polymer was dried under reduced pressureat 80° C. for 6 hr. The polymer was obtained in an amount of 568 g andhad a polymerization activity of 317 Kg-PP/mmol-Zr·hr. In the analysisresults, the polymer had an ethylene content of 3.3 mol % and a [η]value of 1.88 dl/g.

Comparative Example 26c Ethylene/Propylene Bulk Copolymerization

Polymerization was carried out in the same conditions as ComparativeExample 25c except that 1.29 μmol in terms of transition metal compoundof the suspension (0.46 mmol in terms of aluminum of methyl aluminoxane)and 3.44 ml of a heptane solution of EPAN720 (EPAN720=1.91 mg/ml) as anantifouling agent were introduced. The polymer was obtained in an amountof 472 g and had a polymerization activity of 365 Kg-Polymer/mmol-Zr·hr.In the analysis results, the polymer had an ethylene content of 4.3 mol%, a [η] value of 1.76 dl/g and a Tm of 127.7° C. The polymerizationresults are inclusively shown in Table 5c.

TABLE 5c Transition metal compound MAO Polymerization Zr concentrationAl concentration Ethylene time Yield Kind [μmol] [mmol] [Nl] [min] [g]Example 31c A 1.91 0.85 5 60 133 32c A 1.91 0.85 10 60 288 ComparativeExample 25c E 1.79 0.64 10 60 568 26c E 1.29 0.46 10 60 472Polymerization Ethylene content in activity Polymer [η] Tm [Kg/mmol-Zr ·h] [mol %] [dl/g] [° C.] Example 31c 69.5 2.6 2.72 129.7 32c 150 4.42.63 120.7 Comparative Example 25c 317 3.3 1.88 — 26c 365 4.3 1.76 127.7Polymerization conditions: Liquid propylene 1,500 g, Temperature 60° C.,Transition metal compound A:Diphenylmethylene(3-tert-butyl-5-methyl-cyclopentadienyl)(fluorenyl)zirconiumdichloride Transition metal compound E:Dimethylmethylene(3-tert-butyl-5-methyl-cyclopentadienyl)(fluorenyl)zirconiumdichloride

Example 33c Synthesis ofdi(4-tert-butyl-phenyl)methylene(3-tert-butyl-5-methyl-cyclopentadienyl)(fluorenyl)zirconiumdichloride

(1) Synthesis of3-tert-butyl-1-methyl-6,6-di(4-tert-butyl-phenyl)fulvene

In a 200 ml three-necked flask equipped with a magnetic stirrer chip andthree-way cock thoroughly purged with nitrogen, 1.58 g of powderypotassium hydroxide (28.2 mmol) and 100 ml of dehydrated dimethoxyethane were added in a nitrogen atmosphere. To the suspension, 2.31 g of3-tert-butyl-1-methyl-cyclopentadiene (17.0 mmol) was gradually addeddropwise at room temperature and stirred under reflux for 1 hr.Thereafter, a solution prepared by dissolving 5.25 g of4,4′-di-tert-butyl -benzophenone (17.8 mmol) to 40 ml of dehydrateddimethoxyethane was gradually added dropwise and stirred under refluxfor 2 days. To the resulting reaction mixture, 50 ml of a hydrochloricacid aqueous solution (1N) was gradually added dropwise in an ice bathand stirred at room temperature for some time. Diethyl ether was addedto the mixed solution to separate an organic phase. The organic phasewas washed with a saturated sodium bicarbonate aqueous solution, waterand saturated brine. The organic phase was dried with anhydrousmagnesium sulfate, thereafter the drying agent was filtered off and thesolvent was distilled off from the filtrate under reduced pressure togive a reddish-brown solid. The solid was purified with a columnchromatography using 240 g of silica gel (developing solvent: n-hexane)and the developing solvent was distilled off under reduced pressure, andthereby the aimed compound was obtained in an amount of 2.10 g (5.09mmol) as a reddish-orange solid (yield: 30%).

(2) Synthesis of (3-tert-butyl-5-methyl-cyclopentadienyl)(fluorenyl)di(4-tert-butyl-phenyl)methane

In a 200 ml three-necked flask equipped with a magnetic stirrer chip andthree-way cock thoroughly purged with nitrogen, 0.653 g of fluorene(3.93 mmol) was dissolved in 50 ml of dehydrated diethylether in anitrogen atmosphere. To the solution, 2.7 ml of n-butyl lithium/hexanesolution (1.58M: 4.27 mmol) was gradually added dropwise in an ice bathand stirred at room temperature over night. To the solution, a solutionprepared by dissolving 2.09 g of3-tert-butyl-1-methyl-6,6-di(4-tert-butyl-phenyl)fulvene (5.06 mmol) in100 ml of dehydrated diethyl ether was added and stirred under refluxfor 10 days and then stirred at room temperature for 11 days. To thereaction mixture, 30 ml of distilled water was gradually added dropwisein an ice bath, and then diethyl ether was added to separate an organicphase. The organic phase was washed with distilled water and saturatedbrine. The organic phase was dried with anhydrous magnesium sulfate,thereafter the drying agent was filtered off and the solvent wasdistilled off from the filtrate under reduced pressure to give areddish-brown solid. The solid was purified with a column chromatographyusing 150 g of silica gel (developing solvent: n-hexane) and thedeveloping solvent was distilled off under reduced pressure. Theremaining product was re-crystallized using hexane and dried underreduced pressure, and thereby the aimed compound was obtained in anamount of 0.439 g (0.758 mmol) as a pale yellow solid (yield: 19%).

(3) Synthesis ofdi(4-tert-butylphenyl)methylene(3-tert-butyl-5-methyl-cyclopentadienyl)(fluorenyl)zirconiumdichloride

In a 100 ml Schlenk flask equipped with a magnetic stirrer chip andthree-way cock thoroughly purged with nitrogen, 0.450 g of(3-tert-butyl-5-methyl-cyclopentadienyl)(fluorenyl)di(4-tert-butyl-phenyl)methane (0.777 mmol)was dissolved in 10 ml of dehydrated diethylether in a nitrogenatmosphere. To the solution, 1.05 ml of n-butyl lithium/hexane solution(1.58M: 1.66 mmol) was gradually added dropwise in an ice bath andstirred at room temperature over night. The reaction solution was cooledsufficiently in an dry ice/methanol bath and 0.224 g of zirconiumtetrachloride (0.961 mmol) was added. The solution was stirred for 2days while returning the temperature to room temperature. Thereafter,the solvent was distilled off under reduced pressure. The reactionmixture was introduced into a glove box and re-slurried with dehydratedhexane and filtered off using a glass filter filled with diatomaceousearth. The solvent in the filtrate was distilled off to prepare a solid.The solid was washed with a small amount of dehydrated pentane. Thesolvent of the washing liquid was distilled off and the remainingproduct was dried under reduced pressure, and thereby the aimed compoundwas obtained in an amount of 216 mg (0.292 mmol) as a reddish-orangesolid (yield: 38%).

The identification was carried out by ¹H-NMR spectrum and FD-massspectrometry spectrum. The measurement results are shown below.

¹H-NMR spectrum (CDCl₃, TMS standard): /ppm 1.07 (s, 9H), 1.27 (s+s,18H), 1.83 (s, 3H), 5.63 (d, 1H), 6.12-6.17 (m, 2H), 6.80-6.86 (m, 1H),6.93-7.03 (m, 2H), 7.20-7.38 (m, 4H), 7.41-7.48 (m, 2H), 7.60-7.64 (m,1H), 7.71-7.80 (m, 3H), 8.06-8.09 (m, 2H) FD-mass spectrometry spectrum:M/z=738 (M⁺)

Example 34c Synthesis ofdi(4-chloro-phenyl)methylene(3-tert-butyl-5-methyl-cyclopentadienyl)(fluorenyl)zirconiumdichloride

(1) Synthesis of 3-tert-butyl-1-methyl-6,6-di(4-chloro-phenyl)fulvene

In a 200 ml three-necked flask equipped with a magnetic stirrer chip andthree-way cock thoroughly purged with nitrogen, 0.65 g of powderypotassium hydroxide (13.0 mmol) and 70 ml of dehydrated dimethoxy ethanewere added in a nitrogen atmosphere. To the suspension, 1.24 g of3-tert-butyl-1-methyl-cyclopentadiene (9.11 mmol) was added dropwise atroom temperature and then 2.40 g of 4,4′-dichloro-benzophenone (9.58mmol) was added and stirred under reflux for 3 days. To a 30 ml of ahydrochloric acid aqueous solution (1N) set in an ice bath, the reactionmixture was gradually added dropwise and stirred for some time. Diethylether was added to the mixed solution to separate an organic phase. Theorganic phase was washed with a saturated sodium bicarbonate aqueoussolution, water and saturated brine. The organic phase was dried withanhydrous magnesium sulfate, thereafter the drying agent was filteredoff and the solvent was distilled off from the filtrate under reducedpressure to give a reddish-orange solid. The solid was purified with acolumn chromatography using 110 g of silica gel (developing solvent:n-hexane) and the developing solvent was distilled off under reducedpressure, and thereby the aimed compound was obtained in an amount of2.79 g (7.56 mmol) as a red solid (yield: 83%).

(2) Synthesis of(3-tert-butyl-5-methyl-cyclopentadienyl)(fluorenyl)di(4-chloro-phenyl)methane

In a 200 ml three-necked flask equipped with a magnetic stirrer chip andthree-way cock thoroughly purged with nitrogen, 1.42 g of fluorene (8.52mmol) was dissolved in 60 ml of dehydrated diethyl ether in a nitrogenatmosphere. To the solution, 5.6 ml of n-butyl lithium/hexane solution(1.58M: 8.85 mmol) was gradually added dropwise in an ice bath andstirred at room temperature over night. To the reaction solution, 2.99 gof 3-tert-butyl-1-methyl-6,6-di(4-chloro -phenyl)fulvene (8.08 mmol) wasadded and stirred under reflux for several days. The reaction mixturewas gradually added dropwise to 30 ml of a hydrochloric acid aqueoussolution (1N) set in an ice bath, and stirred briefly. Therein, diethylether was added to separate an organic phase. The organic phase waswashed with a saturated sodium bicarbonate aqueous solution, water andsaturated brine. The organic phase was dried with anhydrous magnesiumsulfate, thereafter the drying agent was filtered off and the solventwas distilled off from the filtrate under reduced pressure to give a redsolid. The solid was purified with a column chromatography using 180 gof silica gel (developing solvent: n-hexane) and the developing solventwas distilled off under reduced pressure. Thereafter, the remainingproduct was re-crystallized using hexane and dried under reducedpressure, and thereby the aimed compound was obtained in an amount of1.69 g (3.16 mmol) as a pale yellow solid (yield: 39%).

(3) Synthesis ofdi(4-chloro-phenyl)methylene(3-tert-butyl-5-methyl-cyclopentadienyl)(fluorenyl)zirconiumdichloride

In a 30 ml Schlenk flask equipped with a magnetic stirrer chip andthree-way cock thoroughly purged with nitrogen, 1.12 g of(3-tert-butyl-5-methyl-cyclopentadienyl)(fluorenyl)di(4-chloro-phenyl)methane(2.09 mmol) was dissolved in 20 ml of dehydrated diethylether in anitrogen atmosphere. To the solution, 2.7 ml of n-butyl lithium/hexanesolution (1.58M: 4.27 mmol) was gradually added dropwise in an ice bathand stirred at room temperature over night. The solvent was distilledoff under reduced pressure to prepare a red solid. The solid was washedwith dehydrated hexane and dried under reduced pressure to prepare areddish-orange solid. To the solid, 20 ml of dehydrated diethyl etherwas added and the reaction solution was cooled sufficiently in a dryice/methanol bath and 0.306 g of zirconium tetrachloride (1.31 mmol) wasadded. The solution was stirred for 3 days while gradually returning thetemperature to room temperature. Thereafter, the solvent was distilledoff under reduced pressure. The reaction mixture was introduced into aglove box and re-slurried with dehydrated hexane and filtered off usinga glass filter filled with diatomaceous earth. The filtrate wasconcentrated to prepare a solid. The solid was separated withcentrifugal separator and washed with a small amount of dehydrateddiethyl ether, and thereby the aimed compound was obtained in an amountof 33.9 mg (0.049 mmol) as a reddish-orange solid (yield: 4%).

The identification was carried out by ¹H-NMR spectrum and FD-massspectrometry spectrum. The measurement results are shown below.

¹H-NMR spectrum (CDCl₃, TMS standard): /ppm 1.10 (s, 9H), 1.92 (s, 3H),5.62 (d, 1H), 6.20 (d, 1H), 6.33-6.36 (s+s, 1H), 6.95-7.08 (m, 3H),7.28-7.46 (m, 3H), 7.50-7.56 (m, 2H), 7.68-7.72 (m, 1H), 7.83-7.88 (m,3H), 8.13-8.18 (m, 2H) FD-mass spectrometry spectrum: M/z=694 (M⁺)

Example 35c Synthesis ofdi(3-trifluoromethyl-phenyl)methylene(3-tert-butyl-5-methyl-cyclopentadienyl)(fluorenyl)zirconiumdichloride

(1) Synthesis of3-tert-butyl-1-methyl-6,6-di(3-trifluoromethyl-phenyl)fulvene

In a 200 ml three-necked flask equipped with a magnetic stirrer chip andthree-way cock thoroughly purged with nitrogen, 40 ml of dehydratedtetrahydrofuran and 1.41 g of 3-tert-butyl-1-methyl-cyclopentadiene(10.4 mmol) were added in a nitrogen atmosphere. To the solution, 7.0 mlof n-butyl lithium/hexane solution (1.58M:11.1 mmol) was gradually addeddropwise in an ice bath and stirred at room temperature for 2 days. Tothe reaction solution, 5.4 ml of hexamethyl phosphoramide dried withmolecular sieves 4 A was added dropwise in an ice bath, and stirred atroom temperature for 1 hr. Further, to the solution, 3.49 g of3,3′-di-trifluoromethyl -benzophenone (11.0 mmol) was added and stirredat room temperature for 3 days. To a 30 ml of a hydrochloric acidaqueous solution (EN) set in an ice bath, the reaction mixture wasgradually added dropwise and stirred at room temperature for some time.Diethyl ether was added to the mixed solution to separate an organicphase. The organic phase was washed with a saturated sodium bicarbonateaqueous solution, water and saturated brine. The organic phase was driedwith anhydrous magnesium sulfate, thereafter the drying agent wasfiltered off and the solvent was distilled off from the filtrate underreduced pressure to give a dark red solid. The solid was purified with acolumn chromatography using 140 g of silica gel (developing solvent:n-hexane) and the developing solvent was distilled off under reducedpressure, and thereby the aimed compound was obtained in an amount of3.88 g (8.89 mmol) as a red solid (yield: 86%).

(2) Synthesis of(3-tert-butyl-5-methyl-cyclopentadienyl)(fluorenyl)di(3-trifluoromethyl-phenyl)methane

In a 200 ml three-necked flask equipped with a magnetic stirrer chip andthree-way cock thoroughly purged with nitrogen, 1.44 g of fluorene (8.69mmol) was dissolved in 60 ml of dehydrated diethylether in a nitrogenatmosphere. To the solution, 5.8 ml of n-butyl lithium/hexane solution(1.58M: 9.16 mmol) was gradually added dropwise in an ice bath andstirred at room temperature over night. To the reaction solution, 4.15 gof 3-tert-butyl-1-methyl-6,6-di(3-trifluoromethyl-phenyl)fulvene (9.50mmol) was added and stirred under reflux for several days. The reactionmixture was gradually added dropwise to 30 ml of a hydrochloric acidaqueous solution set (1N) in an ice bath, and stirred at roomtemperature briefly. Therein, diethyl ether was added to separate anorganic phase. The organic phase was washed with distilled water andsaturated brine. The organic phase was dried with anhydrous magnesiumsulfate, thereafter the drying agent was filtered off and the solventwas distilled off from the filtrate under reduced pressure to give adark red solid. The solid was purified with a column chromatographyusing 220 g of silica gel (developing solvent: n-hexane) and thedeveloping solvent was distilled off under reduced pressure. Thereafter,the remaining product was re-crystallized using hexane and dried underreduced pressure, and thereby the aimed compound was obtained in anamount of 1.69 g (2.72 mmol) as a white solid (yield: 31%).

(3) Synthesis of di(3-trifluoromethyl-phenyl)methylene(3-tert-butyl-5-methyl-cyclopentadienyl)(fluorenyl)zirconium dichloride

In a 30 ml Schlenk flask equipped with a magnetic stirrer chip andthree-way cock thoroughly purged with nitrogen, 0.622 g of(3-tert-butyl-5-methyl-cyclopentadienyl)(fluorenyl)di(3-trifluoromethyl-phenyl)methane (1.03 mmol) was dissolved in 20 ml of dehydrated diethylether in a nitrogen atmosphere. To the solution, 1.4 ml of n-butyllithium/hexane solution (1.58M: 2.21 mmol) was gradually added dropwisein an ice bath and stirred at room temperature over night. The reactionsolution was sufficiently cooled by an ice bath and 0.208 g of zirconiumtetrachloride (0.893 mmol) was added. The solution was stirred for 3days while gradually returning the temperature to room temperature.Thereafter, the solvent was distilled off under reduced pressure. Thereaction mixture was introduced into a glove box and re-slurried withdehydrated hexane and filtered off using a glass filter filled withdiatomaceous earth. The filtrate was concentrated to prepare a solid.The solid was separated with centrifugal separator, washed with a smallamount of dehydrated diethyl ether and dried under reduced pressure, andthereby the aimed compound was obtained in an amount of 97.2 mg (0.127mmol) as a reddish-pink solid (yield: 14%).

The identification was carried out by ¹H-NMR spectrum and FD-massspectrometry spectrum. The measurement results are shown below.

¹H-NMR spectrum (CDCl₃, TMS standard): /ppm 1.10-1.12 (s+s, 9H), 1.90(s, 3H), 5.62 (d, 1H), 6.17-6.25 (m, 2H), 6.84-6.87 (m, 1H), 6.95-7.09(m, 2H), 7.42-7.60 (m, 6H), 7.99-8.02 (m, 1H), 8.14-8.20 (m, 5H),FD-mass spectrometry spectrum: M/z=762 (M⁺)

Example 36c Preparation of Supported Catalyst

In a 100 ml three-necked flask thoroughly purged with nitrogen, astirring rod was mounted, and 1.0 g of silica supported methylaluminoxane (Al=7.04 mmol/g) was added. Therein, 10 ml of dehydratedtoluene was added at room temperature and then 20 ml of a toluenesolution of 28.1 μmol ofdiphenylmethylene(3-tert-butyl-5-methyl-cyclopentadienyl)(fluorenyl)zirconiumdichloride synthesized in Example 1c as a transition metal compound wasadded with stirring and stirred for 1 hr. The resulting slurry wasfiltered with a filter, and a powder present on the filter was washedwith 10 ml of dehydrated toluene once and then washed with 10 ml ofdehydrated hexane three times. The powder obtained after washing wasdried under reduced pressure for 1.5 hr and 0.70 g of the powder wasobtained. The powder was mixed with 6.40 g of mineral oil to prepare a9.9 wt % slurry.

Example 37c Propylene/Ethylene Copolymerization

Into a 2000 ml internal volume SUS-made autoclave thoroughly purged withnitrogen, 0.60 L of liquid propylene was fed and heated to 55° C. whilesufficiently stirring. The internal pressure of the autoclave was set to30 Kg/cm²G by pressurization with ethylene gas. Subsequently, to a 30 mlinternal volume catalyst feed pot mounted on the autoclave, which potwas thoroughly purged with nitrogen, a mixed solution of 4 ml ofdehydrated hexane and 1 mmol of a hexane solution of triisobutylaluminum (Al=1.0 mol/l) was added and fed into the autoclave bypressurization with nitrogen. Next to the catalyst feed pot, a mixtureof 340 mg of the supported catalyst slurry prepared in Example 36c and1.0 mmol of a hexane solution of triisobutyl aluminum (Al=1.0 M) wasadded and fed to the autoclave by pressurization with nitrogen, and thenpolymerization was started. The polymerization was carried out for 10min, and then a small amount of methanol was added to stop thepolymerization. The resulting polymer solution was added into excessamounts of methanol mixed with hydrochloric acid and deashed, and thenthe polymer precipitated was separated with filtration. Thereafter, thepolymer was dried under reduced pressure at 80° C. for 10 hr. Thepolymer was obtained in an amount of 22.8 g and had a polymerizationactivity of 151 Kg-Polymer/mmol-Zr·hr. In the analysis results, thepolymer had an ethylene content of 31 mol %, a [η] value of 2.08 dl/g, aMw of 255,000 and a Mw/Mn ratio of 2.4.

Example 38c Propylene/Ethylene Copolymerization

Polymerization was carried out in the same manner as Example 37c exceptthat the internal pressure of the autoclave was set to 35 Kg/cm²G bypressurization with ethylene gas and the polymerization time was 6 min.The polymer was obtained in an amount of 38.5 g and had a polymerizationactivity of 427 Kg-Polymer/mmol-Zr·hr. In the analysis results, thepolymer had an ethylene content of 42 mol % and a [η] value of 2.57dl/g, a Mw of 264,000 and a Mw/Mn ratio of 2.4.

Example 39c Propylene/Ethylene Copolymerization

Polymerization was carried out in the same manner as Example 37c exceptthat the internal pressure of the autoclave was set to 40 Kg/cm²G bypressurization with ethylene gas and 170 mg of the supported catalystslurry prepared in Example 36c was used. The polymer was obtained in anamount of 22.9 g and had a polymerization activity of 304Kg-Polymer/mmol-Zr·hr. In the analysis results, the polymer had anethylene content of 56 mol % and a [η] value of 3.19 dl/g, a Mw of339,000 and a Mw/Mn ratio of 2.3.

Example 40c Preparation of Supported Catalyst

The procedure of Example 36c was repeated except that 0.8 g of silicasupported methyaluminoxane (Al=7.04 mmol/g) and 4.8 ml of a toluenesolution of 22.1 μmol ofdiphenylmethylene(3-tert-butyl-5-methyl-cyclopentadienyl)(3,6-di-tert-butyl-fluorenyl)zirconiumdichloride were used, and 0.91 g of a powder was obtained. The powderwas mixed with 8.08 g of mineral oil to prepare a 10.1 wt % slurry.

Example 41c Propylene/Ethylene Copolymerization

Polymerization was carried out in the same manner as Example 37c exceptthat 340 mg of the supported catalyst slurry prepared in Example 40c wasused a supported catalyst. The polymer was obtained in an amount of 4.8g and had a polymerization activity of 31 Kg-Polymer/mmol-Zr·hr. In theanalysis results, the polymer had an ethylene content of 27 mol %, a [η]value of 1.64 dl/g, a Mw of 153,000 and a Mw/Mn ratio of 2.2.

Example 42c Propylene/Ethylene Copolymerization

Polymerization was carried out in the same manner as Example 37c exceptthat the internal pressure of the autoclave was set to 35 Kg/cm²G bypressurization with ethylene gas and 340 mg of the supported catalystslurry prepared in Example 40c was used. The polymer was obtained in anamount of 16.4 g and had a polymerization activity of 106Kg-Polymer/mmol-Zr·hr. In the analysis results, the polymer had anethylene content of 40 mol % and a [η] value of 1.68 dl/g, a Mw of137,000 and a Mw/Mn ratio of 2.4.

Example 43c Propylene/Ethylene Copolymerization

Polymerization was carried out in the same manner as Example 37c exceptthat the internal pressure of the autoclave was set to 40 Kg/cm²G bypressurization with ethylene gas and 170 mg of the supported catalystslurry prepared in Example 40c was used. The polymer was obtained in anamount of 10.8 g and had a polymerization activity of 139Kg-Polymer/mmol-Zr·hr. In the analysis results, the polymer had anethylene content of 57 mol % and a [η] value of 2.27 dl/g, a Mw of195,000 and a Mw/Mn ratio of 2.1.

Example 44c Preparation of Supported Catalyst

The procedure of Example 36c was repeated except that 1.1 g of silicasupported methyl aluminoxane (Al=7.04 mmol/g) and 7.0 ml of a toluenesolution of 29.2 μmol of diphenylmethylene(3-tert-butyl-5-methyl-cyclopentadienyl(2,7-di-tert-butyl-fluorenyl)zirconiumdichloride were used, and 0.95 g of a powder was obtained. The powderwas mixed with 8.51 g of mineral oil to prepare a 10.0 wt % slurry.

Example 45c Propylene/Ethylene Copolymerization

Polymerization was carried out in the same manner as Example 37c exceptthat 340 mg of the supported catalyst slurry prepared in Example 44c wasused as a supported catalyst and the polymerization time was 8 min. Thepolymer was obtained in an amount of 16.7 g and had a polymerizationactivity of 136 Kg-Polymer/mmol-Zr·hr. In the analysis results, thepolymer had an ethylene content of 34 mol %, a [η] value of 3.49 dl/g, aMw of 425,000 and a Mw/Mn ratio of 2.2.

Example 46c Propylene/Ethylene Copolymerization

Polymerization was carried out in the same manner as Example 37c exceptthat the internal pressure of the autoclave was set to 35 Kg/cm²G bypressurization with ethylene gas and 340 mg of the supported catalystslurry prepared in Example 44c was used. The polymer was obtained in anamount of 41.7 g and had a polymerization activity of 272Kg-Polymer/mmol-Zr·hr. In the analysis results, the polymer had anethylene content of 44 mol % and a [η] value of 3.77 dl/g, a Mw of466,000 and a Mw/Mn ratio of 2.3.

Example 47c Propylene/Ethylene Copolymerization

Polymerization was carried out in the same manner as Example 37c exceptthat the internal pressure of the autoclave was set to 40 Kg/cm²G bypressurization with ethylene gas and 170 mg of the supported catalystslurry prepared in Example 44c was used. The polymer was obtained in anamount of 12.8 g and had a polymerization activity of 167Kg-Polymer/mmol-Zr·hr. In the analysis results, the polymer had anethylene content of 56 mol % and a [η] value of 4.51 dl/g, a Mw of598,000 and a Mw/Mn ratio of 2.5.

Example 48c Preparation of Supported Catalyst

The procedure of Example 36c was repeated except that 1.0 g of silicasupported methyl aluminoxane (Al=7.04 mmol/g) and 7.7 ml of a toluenesolution of 32.7 μmol ofdi(p-tolyl)methylene(3-tert-butyl-5-methyl-cyclopentadienyl)(fluorenyl)zirconiumdichloride were used, and 0.96 g of a powder was obtained. The powderwas mixed with 8.53 g of mineral oil to prepare a 10.1 wt % slurry.

Example 49c Propylene/Ethylene Copolymerization

Polymerization was carried out in the same manner as Example 37c exceptthat 340 mg of the supported catalyst slurry prepared in Example 48c wasused as a supported catalyst. The polymer was obtained in an amount of21.3 g and had a polymerization activity of 122 Kg-Polymer/mmol-Zr·hr.In the analysis results, the polymer had an ethylene content of 37 mol%, a [η] value of 2.68 dl/g, a Mw of 324,000 and a Mw/Mn ratio of 2.3.

Example 50c Propylene/Ethylene Copolymerization

Polymerization was carried out in the same manner as Example 37c exceptthat the internal pressure of the autoclave was set to 35 Kg/cm²G bypressurization with ethylene gas and 340 mg of the supported catalystslurry prepared in Example 48c was used. The polymer was obtained in anamount of 23.9 g and had a polymerization activity of 137Kg-Polymer/mmol-Zr·hr. In the analysis results, the polymer had anethylene content of 47 mol % and a [η] value of 2.87 dl/g, a Mw of318,000 and a Mw/Mn ratio of 2.3.

Example 51c Propylene/Ethylene Copolymerization

Polymerization was carried out in the same manner as Example 37c exceptthat the internal pressure of the autoclave was set to 40 Kg/cm²G bypressurization with ethylene gas and 170 mg of the supported catalystslurry prepared in Example 48c was used. The polymer was obtained in anamount of 14.7 g and had a polymerization activity of 169Kg-Polymer/mmol-Zr·hr. In the analysis results, the polymer had anethylene content of 56 mol % and a [η] value of 3.40 dl/g, a Mw of373,000 and a Mw/Mn ratio of 2.6.

Example 52c Preparation of Supported Catalyst

The procedure of Example 36c was repeated except that 1.1 g of silicasupported methyl aluminoxane (Al=7.04 mmol/g) and 20 ml of a toluenesolution of 21.1 μmol ofdi(4-tert-butyl-phenyl)methylene(3-tert-butyl-5-methyl-cyclopentadienyl)(fluorenyl)zirconiumdichloride synthesized in Example 33C were used, and 0.94 g of a powderwas obtained. The powder was mixed with 8.29 g of mineral oil to preparea 10.1 wt % slurry.

Example 53c Propylene/Ethylene Copolymerization

Polymerization was carried out in the same manner as Example 37c exceptthat 340 mg of the supported catalyst slurry prepared in Example 52c wasused as a supported catalyst. The polymer was obtained in an amount of32.2 g and had a polymerization activity of 227 Kg-Polymer/mmol-Zr·hr.In the analysis results, the polymer had an ethylene content of 25 mol%, a [η] value of 2.05 dl/g, a Mw of 321,000 and a Mw/Mn ratio of 2.3.

Example 54c Propylene/Ethylene Copolymerization

Polymerization was carried out in the same manner as Example 37c exceptthat the internal pressure of the autoclave was set to 35 Kg/cm²G bypressurization with ethylene gas and 170 mg of the supported catalystslurry prepared in Example 52c was used. The polymer was obtained in anamount of 17.3 g and had a polymerization activity of 243Kg-Polymer/mmol-Zr·hr. In the analysis results, the polymer had anethylene content of 39 mol % and a [η] value of 2.90 dl/g, a Mw of317,000 and a Mw/Mn ratio of 2.2.

Example 55c Propylene/Ethylene Copolymerization

Polymerization was carried out in the same manner as Example 37c exceptthat the internal pressure of the autoclave was set to 40 Kg/cm²G bypressurization with ethylene gas and 170 mg of the supported catalystslurry prepared in Example 52c was used. The polymer was obtained in anamount of 27.1 g and had a polymerization activity of 381Kg-Polymer/mmol-Zr·hr. In the analysis results, the polymer had anethylene content of 56 mol % and a [η] value of 3.03 dl/g, a Mw of374,000 and a Mw/Mn ratio of 2.4.

Example 56c Preparation of Supported Catalyst

The procedure of Example 36c was repeated except that 1.0 g of silicasupported methyl aluminoxane (Al=7.04 mmol/g) and 20 ml of a toluenesolution of 29.2 μmol ofdi(4-chloro-phenyl)methylene(3-tert-butyl-5-methyl-cyclopentadienyl)(fluorenyl)zirconiumdichloride were used, and 0.99 g of a powder was obtained. The powderwas mixed with 9.87 g of mineral oil to prepare a 10.0 wt % slurry.

Example 57c Propylene/Ethylene Copolymerization

Polymerization was carried out in the same manner as Example 37c exceptthat 340 mg of the supported catalyst slurry prepared in Example 56c wasused a supported catalyst and the polymerization time was 15 min. Thepolymer was obtained in an amount of 6.6 g and had a polymerizationactivity of 26 Kg-Polymer/mmol-Zr·hr. In the analysis results, thepolymer had an ethylene content of 28 mol %, a [η] value of 1.71 dl/g, aMw of 205,000 and a Mw/Mn ratio of 2.6.

Example 58c Propylene/Ethylene Copolymerization

Polymerization was carried out in the same manner as Example 37c exceptthat the internal pressure of the autoclave was set to 35 Kg/cm²G bypressurization with ethylene gas and 340 mg of the supported catalystslurry prepared in Example 56c was used. The polymer was obtained in anamount of 8.2 g and had a polymerization activity of 49Kg-Polymer/mmol-Zr·hr. In the analysis results, the polymer had anethylene content of 45 mol % and a [η] value of 2.03 dl/g, a Mw of201,000 and a Mw/Mn ratio of 2.6.

Example 59c Propylene/Ethylene Copolymerization

Polymerization was carried out in the same manner as Example 37c exceptthat the internal pressure of the autoclave was set to 40 Kg/cm²G bypressurization with ethylene gas and 340 mg of the supported catalystslurry prepared in Example 56c was used. The polymer was obtained in anamount of 14.7 g and had a polymerization activity of 88Kg-Polymer/mmol-Zr·hr. In the analysis results, the polymer had anethylene content of 59 mol % and a [η] value of 2.78 dl/g, a Mw of234,000 and a Mw/Mn ratio of 2.5.

Example 60c Preparation of Supported Catalyst

The procedure of Example 36c was repeated except that 1.1 g of silicasupported methyl aluminoxane (Al=7.04 mmol/g) and 20 ml of a toluenesolution of 29.4 μmol ofdi(3-trifluoromethyl-phenyl)methylene(3-tert-butyl-5-methyl-cyclopentadienyl)(fluorenyl)zirconiumdichloride as a transition metal compound were used, and 0.96 g of apowder was obtained. The powder was mixed with 10.1 g of mineral oil toprepare a 9.6 wt % slurry.

Example 61c Propylene/Ethylene Copolymerization

Polymerization was carried out in the same manner as Example 37c exceptthat 354 mg of the supported catalyst slurry prepared in Example 60c wasused as a supported catalyst. The polymer was obtained in an amount of6.0 g and had a polymerization activity of 40 Kg-Polymer/mmol-Zr·hr. Inthe analysis results, the polymer had an ethylene content of 31 mol %, a[η] value of 2.05 dl/g, a Mw of 246,000 and a Mw/Mn ratio of 2.9.

Example 62c Propylene/Ethylene Copolymerization

Polymerization was carried out in the same manner as Example 37c exceptthat the internal pressure of the autoclave was set to 35 Kg/cm²G bypressurization with ethylene gas and 354 mg of the supported catalystslurry prepared in Example 60c was used. The polymer was obtained in anamount of 8.1 g and had a polymerization activity of 54Kg-Polymer/mmol-Zr·hr. In the analysis results, the polymer had anethylene content of 50 mol % and a [η] value of 3.53 dl/g, a Mw of322,000 and a Mw/Mn ratio of 2.7.

Example 63c Propylene/Ethylene Copolymerization

Polymerization was carried out in the same manner as Example 37c exceptthat the internal pressure of the autoclave was set to 40 Kg/cm²G bypressurization with ethylene gas and 354 mg of the supported catalystslurry prepared in Example 60c was used. The polymer was obtained in anamount of 5.8 g and had a polymerization activity of 38Kg-Polymer/mmol-Zr·hr. In the analysis results, the polymer had anethylene content of 61 mol % and a [η] value of 3.39 dl/g, a Mw of389,000 and a Mw/Mn ratio of 3.1.

Comparative Example 27c Preparation of Supported Catalyst

In a 100 ml three-necked flask thoroughly purged with nitrogen, astirring rod was mounted, and 1.0 g of silica supported methylaluminoxane (Al=7.04 mmol/g) was added. Therein, 10 ml of dehydratedtoluene was added at room temperature and then 20 ml of a toluenesolution of 41.0 μmol ofdimethylmethylene(3-tert-butyl-5-methyl-cyclopentadienyl)(fluorenyl)zirconiumdichloride synthesized in the method disclosed in the pamphlet ofWO01/27124 as a transition metal compound was added with stirring andstirred for 1 hr. The resulting slurry was filtered, and a powderpresent on the filter was washed with 10 ml of dehydrated toluene onceand then washed with 10 ml of dehydrated hexane three times. The powderobtained after washing was dried under reduced pressure for 1 hr and0.91 g of the powder was obtained. The powder was mixed with 8.14 g ofmineral oil to prepare a 10.0 wt % slurry.

Comparative Example 28c Propylene/Ethylene Copolymerization

Into a 2000 ml internal volume SUS-made autoclave thoroughly purged withnitrogen, 0.60 L of liquid propylene was fed and heated to 55° C. whilesufficiently stirring. The internal pressure of the autoclave was set to30 Kg/cm²G by pressurization with ethylene gas. Successively, to a 30 mlinternal volume catalyst feed pot mounted on the autoclave, which potwas thoroughly purged with nitrogen, a mixed solution of 4 ml ofdehydrated hexane and 1 ml of a hexane solution of triisobutyl aluminum(Al=1.0 mol/l) was added and fed into the autoclave by pressurizationwith nitrogen. Next, to the catalyst feed pot, a mixture of 340 mg ofthe supported catalyst slurry prepared in Comparative Example 27c and1.0 mmol of a hexane solution of triisobutyl aluminum (Al=1.0 M) wasadded and fed by pressurization with nitrogen, and then polymerizationwas started. The polymerization was carried out for 4 min, and then asmall amount of methanol was added to stop the polymerization. Theresulting polymer was added into excess amounts of methanol mixed withhydrochloric acid and deashed, and then the polymer was separated withfiltration. Thereafter, the polymer was dried under reduced pressure at80° C. for 10 hr. The polymer was obtained in an amount of 18.1 g andhad a polymerization activity of 201 Kg-Polymer/mmol-Zr·hr. In theanalysis results, the polymer had an ethylene content of 31 mol %, a [η]value of 0.85 dl/g, a Mw of 85,000 and a Mw/Mn ratio of 1.9.

Comparative Example 29c Propylene/Ethylene Copolymerization

Polymerization was carried out in the same manner as Comparative Example28c except that the internal pressure of the autoclave was set to 35Kg/cm²G by pressurization with ethylene gas, 170 mg of the supportedcatalyst slurry prepared in Comparative Example 27c was used and thepolymerization time was 10 min. The polymer was obtained in an amount of19.6 g and had a polymerization activity of 174 Kg-Polymer/mmol-Zr·hr.In the analysis results, the polymer had an ethylene content of 39 mol %and a [η] value of 1.00 dl/g, a Mw of 74,000 and a Mw/Mn ratio of 2.0.

Comparative Example 30c Propylene/Ethylene Copolymerization

Polymerization was carried out in the same manner as Comparative Example28c except that the internal pressure of the autoclave was set to 40Kg/cm²G by pressurization with ethylene gas, 170 mg of the supportedcatalyst slurry prepared in Comparative Example 27c was used and thepolymerization time was 10 min. The polymer was obtained in an amount of29.0 g and had a polymerization activity of 257 Kg-Polymer/mmol-Zr·hr.In the analysis results, the polymer had an ethylene content of 49 mol %and a [η] value of 1.00 dl/g, a Mw of 80,000 and a Mw/Mn ratio of 2.1.

Comparative Example 31c Preparation of Supported Catalyst

The procedure of Comparative Example 27c was repeated except that 1.1 gof silica supported methyl aluminoxane (Al=7.04 mmol/g) and 20 ml of atoluene solution of 32.5 μmol ofdimethylmethylene(3-tert-butyl-5-methyl-cyclopentadienyl)(3,6-di-tert-butyl-fluorenyl)zirconiumdichloride synthesized in the method disclosed in the pamphlet ofWO01/27124, as a transition metal compound were used, and 0.81 g of apowder was obtained. The powder was mixed with 7.30 g of mineral oil toprepare a 10.0 wt % slurry.

Comparative Example 32c Propylene/Ethylene Copolymerization

Polymerization was carried out in the same manner as Comparative Example28c except that 340 mg of the supported catalyst slurry prepared inComparative Example 31c was used as a supported catalyst and thepolymerization time was 10 min. The polymer was obtained in an amount of23.9 g and had a polymerization activity of 141 Kg-Polymer/mmol-Zr·hr.In the analysis results, the polymer had an ethylene content of 30 mol%, a [η] value of 0.61 dl/g, a Mw of 36,000 and a Mw/Mn ratio of 1.8.

Comparative Example 33c Propylene/Ethylene Copolymerization

Polymerization was carried out in the same manner as Comparative Example28c except that the internal pressure of the autoclave was set to 35Kg/cm²G by pressurization with ethylene gas, 170 mg of the supportedcatalyst slurry prepared in Comparative Example 31c was used and thepolymerization time was 10 min. The polymer was obtained in an amount of31.0 g and had a polymerization activity of 367 Kg-Polymer/mmol-Zr·hr.In the analysis results, the polymer had an ethylene content of 39 mol %and a [η] value of 0.64 dl/g, a Mw of 41,000 and a Mw/Mn ratio of 1.9.

Comparative Example 34c Propylene/Ethylene Copolymerization

Polymerization was carried out in the same manner as Comparative Example28c except that the internal pressure of the autoclave was set to 40Kg/cm²G by pressurization with ethylene gas, 170 mg of the supportedcatalyst slurry prepared in Comparative Example 31c was used and thepolymerization time was 10 min. The polymer was obtained in an amount of9.9 g and had a polymerization activity of 117 Kg-Polymer/mmol-Zr·hr. Inthe analysis results, the polymer had an ethylene content of 60 mol %and a [η] value of 0.73 dl/g, a Mw of 52,000 and a Mw/Mn ratio of 2.1.

The polymerization results are inclusively shown in Table 6c.

TABLE 6c Transition metal compound MAO PolymeriZation PolymeriZation Zrconcentration Al concentration pressure time Yield Kind [μmol] [mmol][Kg/cm²G] [min] [g] Example 37c A 0.90 0.24 30 10 22.8 38c A 0.90 0.1235 6 38.5 39c A 0.45 0.12 40 10 22.9 41c B 0.93 0.24 30 10 4.8 42c B0.93 0.12 35 10 16.4 43c B 0.47 0.12 40 10 10.8 45c C 0.92 0.24 30 816.7 46c C 0.92 0.24 35 10 41.7 47c C 0.46 0.12 40 10 12.8 49c D 1.050.24 30 10 21.3 50c D 1.05 0.24 35 10 23.9 51c D 0.52 0.12 40 10 14.753c H 0.85 0.24 30 10 32.2 54c H 0.43 0.12 35 10 17.3 55c H 0.43 0.12 4010 27.1 57c I 1.0 0.24 30 15 6.6 58c I 1.0 0.24 35 10 8.2 59c I 1.0 0.2440 10 14.7 61c J 0.91 0.24 30 10 6.0 62c J 0.91 0.24 35 10 8.1 63c J0.91 0.24 40 10 5.8 Comparative Example 28c E 1.35 0.24 30 4 18.1 29c E0.68 0.12 35 10 19.6 30c E 0.68 0.12 40 10 29.0 32c F 1.01 0.24 30 1023.9 33c F 0.51 0.12 35 10 31.0 34c F 0.51 0.12 40 10 9.9 EthylenePolymeriZation Content in activity polymer [η] Mw Mw/Mn [kg/mmol-Zr · h][mol] [dl/g] [×10³] [—] Example 37c 151 31 2.08 255 2.4 38c 427 42 2.57264 2.4 39c 304 56 3.19 339 2.3 41c 31 27 1.64 153 2.2 42c 106 40 1.68137 2.4 43c 139 57 2.27 195 2.1 45c 136 34 3.49 425 2.2 46c 272 44 3.77466 2.3 47c 167 56 4.51 598 2.5 49c 122 37 2.68 324 2.3 50c 137 47 2.87318 2.3 51c 169 56 3.40 373 2.6 53c 227 25 2.05 321 2.3 54c 243 39 2.90317 2.2 55c 381 56 3.03 374 2.4 Example Ex 57c 26 28 1.71 205 2.6 58c 4945 2.03 201 2.6 59c 88 59 2.78 234 2.5 Example 61c 40 31 2.05 246 2.962c 54 50 3.53 322 2.7 63c 38 61 3.39 389 3.1 Comparative Example Com28c 201 31 0.85 85 1.9 29c 174 39 1.00 74 2.0 30c 257 49 1.00 80 2.1Comparative Example 32c 141 30 0.61 36 1.8 33c 367 39 0.64 41 1.9 34c117 60 0.73 52 2.1 Polymerization conditions: Liquid propylene 300 g,Temperature 55° C. or higher, Triisobutyl aluminum 1.0 × 2 mmol.Transition metal compound A:Diphenylmethylene(3-tert-butyl-5-methyl-cyclopentadienyl)(fluorenyl)zirconiumdichloride Transition metal compound B:Diphenylmethylene(3-tert-butyl-5-methyl-cyclopentadienyl)(3,6-di-tert-butyl-fluorenyl)zirconiumdichloride Transition metal compound C:Diphenylmethylene(3-tert-butyl-5-methyl-cyclopentadienyl)(2,7-di-tert-butyl-fluorenyl)zirconiumdichloride Transition metal compound D:Di(p-tolyl)methylene(3-tert-butyl-5-methyl-cyclopentadienyl)(fluorenyl)zirconiumdichloride Transition metal compound E:Dimethylmethylene(3-tert-butyl-5-methyl-cyclopentadienyl)(fluorenyl)zirconiumdichloride Transition metal compound F:Dimethylmethylene(3-tert-butyl-5-methyl-cyclopentadienyl)(3,6-di-tert-butyl-fluorenyl)zirconiumdichloride Transition metal compound H:Di(4-tert-butyl-phenyl)methylene(3-tert-butyl-5-methyl-cyclopentadienyl)(fluorenyl)zirconiumdichloride Transition metal compound I:Di(4-chloro-phenyl)methylene(3-tert-butyl-5-methyl-cyclopentadienyl)(fluorenyl)zirconiumdichloride Transition metal compound J:Di(3-trifluoromethyl-phenyl)methylene(3-tert-butyl-5-methyl-cyclopentadienyl)(fluorenyl)zirconiumdichloride

Example 64c Propylene Bulk Polymerization

Polymerization was carried out in the same conditions as Example 27cexcept that 680 mg of the supported catalyst slurry prepared in Example44c was used. The polymer obtained was 62 g of isotactic polypropyleneand had a polymerization activity of 51 Kg-PP/mmol-Zr·hr. In theanalysis results, the polymer had a [η] value of 3.28 dl/g, a Mw of566,000 and a Mw/Mn ratio of 2.8 and a Tm of 144.8° C.

Example 65c Propylene Bulk Polymerization

Polymerization was carried out in the same conditions as Example 28cexcept that 340 mg of the supported catalyst slurry prepared in Example44c was used. The polymer obtained was 124 g of isotactic polypropyleneand had a polymerization activity of 203 Kg-PP/mmol-Zr·hr. In theanalysis results, the polymer had a [η] value of 1.03 dl/g, a Mw of94,000 and a Mw/Mn ratio of 2.3 and a Tm of 146.2° C.

Example 66c Propylene Bulk Polymerization

Polymerization was carried out in the same conditions as Example 27cexcept that 1020 mg of the supported catalyst slurry prepared in Example48c was used. The polymer obtained was 78 g of isotactic polypropyleneand had a polymerization activity of 37 Kg-PP/mmol-Zr·hr. In theanalysis results, the polymer had a [η] value of 3.03 dl/g, a Mw of553,000 and a Mw/Mn ratio of 3.2 and a Tm of 139.5° C.

Example 67c Propylene Bulk Polymerization

Polymerization was carried out in the same conditions as Example 28cexcept that 340 mg of the supported catalyst slurry prepared in Example48c was used. The polymer obtained was 52 g of isotactic polypropyleneand had a polymerization activity of 75 Kg-PP/mmol-Zr·hr. In theanalysis results, the polymer had a [η] value of 1.05 dl/g, a Mw of97,000 and a Mw/Mn ratio of 2.3 and a Tm of 142.1° C.

Example 68c Propylene Bulk Polymerization

Polymerization was carried out in the same conditions as Example 27cexcept that 1020 mg of the supported catalyst slurry prepared in Example52c was used. The polymer obtained was 125 g of isotactic polypropyleneand had a polymerization activity of 73 Kg-PP/mmol-Zr·hr. In theanalysis results, the polymer had a [η] value of 2.93 dl/g, a Mw of366,000 and a Mw/Mn ratio of 2.7 and a Tm of 141.0° C.

Example 69c Propylene Bulk Polymerization

Polymerization was carried out in the same conditions as Example 28cexcept that 340 mg of the supported catalyst slurry prepared in Example52c was used. The polymer obtained was 137 g of isotactic polypropyleneand had a polymerization activity of 241 Kg-PP/mmol-Zr·hr. In theanalysis results, the polymer had a [η] value of 1.09 dl/g, a Mw of85,000 and a Mw/Mn ratio of 2.3 and a Tm of 142.6° C.

Example 70c Propylene Bulk Polymerization

Polymerization was carried out in the same conditions as Example 27cexcept that 1020 mg of the supported catalyst slurry prepared in Example56c was used. The polymer obtained was 34 g of isotactic polypropyleneand had a polymerization activity of 17 Kg-PP/mmol-Zr·hr. In theanalysis results, the polymer had a [η] value of 3.46 dl/g, a Mw of547,000 and a Mw/Mn ratio of 2.7 and a Tm of 137.2° C.

Example 71c Propylene Bulk Polymerization

Polymerization was carried out in the same conditions as Example 28cexcept that 340 mg of the supported catalyst slurry prepared in Example56c was used. The polymer obtained was 15 g of isotactic polypropyleneand had a polymerization activity of 23 Kg-PP/mmol-Zr·hr. In theanalysis results, the polymer had a [η] value of 1.10 dl/g, a Mw of113,000 and a Mw/Mn ratio of 2.3 and a Tm of 140.3° C.

Example 72c Propylene Bulk Polymerization

Polymerization was carried out in the same conditions as Example 27cexcept that 980 mg of the supported catalyst slurry prepared in Example60c was used. The polymer obtained was 29 g of isotactic polypropyleneand had a polymerization activity of 18 Kg-PP/mmol-Zr·hr. In theanalysis results, the polymer had a [η] value of 3.60 dl/g, a Mw of613,000 and a Mw/Mn ratio of 3.2 and a Tm of 141.7° C.

Example 73c Propylene Bulk Polymerization

Polymerization was carried out in the same conditions as Example 28cexcept that 355 mg of the supported catalyst slurry prepared in Example60c was used. The polymer obtained was 41 g of isotactic polypropyleneand had a polymerization activity of 68 Kg-PP/mmol-Zr·hr. In theanalysis results, the polymer had a [η] value of 1.04 dl/g, a Mw of107,000 and a Mw/Mn ratio of 2.4 and a Tm of 146.7° C. Thepolymerization results are inclusively shown in Table 7c.

TABLE 7c Transition metal compound MAO PolymeriZation Zr concentrationAl concentration Hydrogen time Yield Kind [μmol] [mmol] [Nl] [min] [g]Exa 64c C 1.84 0.48 — 40 62 65c C 0.92 0.24 0.3 40 124 66c D 3.14 0.72 —40 78 67c D 1.05 0.24 0.3 40 52 Ex 68c H 2.55 0.72 — 40 125 69c H 0.850.24 0.3 40 137 70c I 3.01 0.72 — 40 34 71c I 1.00 0.24 0.3 40 15 72c J2.50 0.66 — 40 29 73c J 0.91 0.24 0.3 40 41 PolymeriZation activity [η]Mw Mw/Mn Tm [kg/mmol-Zr · h] [dl/g] [×10³] [—] [° C.] Example 64c 513.28 566 2.8 144.8 65c 203 1.03 94 2.3 146.2 66c 37 3.03 553 3.2 139.567c 75 1.05 97 2.3 142.1 68c 73 2.93 366 2.7 141.0 69c 241 1.09 85 2.3142.6 70c 17 3.46 547 2.7 137.2 71c 23 1.10 113 2.3 140.3 72c 18 3.60613 3.2 141.7 73c 68 1.04 107 2.4 146.7 Polymerization conditions:Liquid propylene 500 g, Temperature 70° C., Triisobutyl aluminum 1.0mmol. Transition metal compound C:Diphenylmethylene(3-tert-butyl-5-methyl-cyclopentadienyl)(2,7-di-tert-butyl-fluorenyl)zirconiumdichloride Transition metal compound D:Di(p-tolyl)methylene(3-tert-butyl-5-methyl-cyclopentadienyl)(fluorenyl)zirconiumdichloride Transition metal compound H:Di(4-tert-butyl-phenyl)methylene(3-tert-butyl-5-methyl-cyclopentadienyl)(fluorenyl)zirconiumdichloride Transition metal compound I:Di(4-chloro-phenyl)methylene(3-tert-butyl-5-methyl-cyclopentadienyl)(fluorenyl)zirconiumdichloride Transition metal compound J:Di(3-trifluoromethyl-phenyl)methylene(3-tert-butyl-5-methyl-cyclopentadienyl)(fluorenyl)zirconiumdichloride

Examples and Comparative Examples of the polyolefin resin composition(CC-3) are described blow.

Example 1d Synthesis of Metallocene Compound

<Synthesis of dimethylmethylene(3-tert-butyl-5-methylcyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirconium dichloride>

In accordance with the examples disclosed in the pamphlet of WO01/27124,dimethylmethylene(3-tert-butyl-5-methylcyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirconium dichloride wasprepared.

<Synthesis of dimethylsilylene bis(2-methyl-4-phenylindenyl)zirconiumdichloride>

In accordance with the method disclosed in Organometallics, 13, 954(1994), dimethylsilylene bis(2-methyl-4-phenylindenyl)zirconiumdichloride was synthesized.

Preparation of Silica Supported Methyl Aluminoxane

To a 500 ml volume reactor thoroughly purged with nitrogen, 20 g ofsilica (Asahi glass Co., Ltd. Trade Name H-121 dried at 150° C. undernitrogen for 4 hr) and 200 ml of toluene were fed and then 60 ml ofmethyl aluminoxane (Albemar Co., Ltd. 10 wt % toluene solution) wasadded dropwise in a nitrogen atmosphere with stirring. After thereaction of this mixture at 110° C. for 4 hr, the reaction system wasallowed to stand for cool to precipitate a solid component. Thesupernatant liquid was removed by decantation. Successively, the solidcomponent was washed with toluene three times and with hexane threetimes to prepare a silica supported methyl aluminoxane.

Production of Polyolefin Resin Composition (CC-3)

To a 20 L volume autoclave thoroughly purged with nitrogen, 20 mmol interms of aluminum of silica supported methyl aluminoxane was fed andsuspended in 500 ml of heptane. Subsequently, to the suspension, atoluene solution of 54 mg (0.088 mmol) ofdimethylmethylene(3-tert-butyl-5-methylcyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirconium dichloride wasadded, and then triisobutyl aluminum (80 mmol) was added and stirred for30 min to prepare a catalyst suspension.

To a 20 L internal volume autoclave thoroughly purged with nitrogen, 5Kg of propylene and 3 L of hydrogen were fed and the above catalystsuspension was added, and bulk homopolymerization was carried out at 70°C. under a pressure of from 3.0 to 3.5 Mpa for 40 min. After completionof the homopolymerization, the vent valve was opened and the unreactedpropylene was vented until the pressure inside the polymerizationreactor was to atmospheric pressure. The yield of the propylene polymerpart (PP-C-i) thus prepared was 2.05 Kg. The polymer part (PP-C-i) had aMFR (ASTM D1238, 230° C., 2.16 Kg load) of 36 g/10 min, a melting point(Tm) of 158° C., a weight average molecular weight (Mw) of 1400,000, anumber average molecular weight (Mn) of 70,000 and a Mw/Mn ratio of 2.0.Further, concerning to stereo-regularity, the polymer part had a mmmmfraction of 95.8%, and 2,1-insertion and 1,3-insertion were notdetected.

To a 20 L internal volume autoclave thoroughly purged with nitrogen, thecatalyst suspension was added and copolymerization of ethylene andpropylene was carried out. That is, an ethylene/propylene mixed gas(ethylene 25 mol %, propylene 75 mol %) was continuously fed andpolymerization was carried out at 70° C. for 120 min, while the openingof the vent valve of the polymerization reactor was regulated so thatthe pressure of the polymerization reactor was 1 Mpa. Adding a smallamount of methanol, the polymerization was stopped and unreacted gas inthe polymerizer was purged. The yield of the elastomer (EL-i) thusprepared was 0.65 Kg. The elastomer (EL-i) had an intrinsic viscosity[η], as measured in decalin at 135° C., of 2.2 dl/g, and an ethylenecontent of 75 mol %. The elastomer (EL-i) had a weight average molecularweight (Mw) of 195,000, an number average molecular weight (Mn) of90,000 and a Mw/Mn ratio of 2.2. Further, 2,1-insertion based onpropylene monomer was not detected.

Production of Polyolefin Resin Composition

The propylene polymer part (PP-C-i) thus prepared, the elastomer (EL-i),an inorganic filler (C-i) [talc, manufactured by Hayashi Chemical Co.,Ltd, K-1 (Trade Mark), average particle diameter 2 μm], Irganox 1010(Trade Mark) [antioxidant manufactured by Ciba Geigy], Irgafos 168(Trade Mark) [antioxidant manufactured by Ciba Geigy], ADK-STAB LA-52(Trade Mark) [hindered amine stabilizer, molecular weight=847manufactured by Asahi Denka Co., Ltd] and calcium stearate were mixed inthe proportion as shown in Table 1d by a tumbler mixer, and thereaftermelt-kneaded by a twi-screw extruder and pelletized.

The polyolefin resin composition (I) thus prepared was injection moldedusing a injection molding machine [manufactured by Niigata Iron WorksCo., Ltd, AN100] into a flat plate (100 mm×300 mm×3 mm thick) and flowmarks were observed. Further, using a injection molding machine(manufactured by Toshiba Machine Co., Ltd, IS100), an ASTM specimen wasinjection molded and the various physical properties thereof weremeasured. The results are shown in Table 1d.

The methods for measuring the physical properties are as follows.

Tensile Properties

With regard to tensile properties, a tensile test was carried out inaccordance with ASTM D638-84 and the tensile elongation was measured inthe following conditions.

<Test Conditions>

-   Test specimen: ASTM D 638-84 No. 1 dumbbell-   Chuck distance: 114 mm-   Temperature: 23° C.-   Tensile rate: 10 mm/min    Flexural Properties

With regard to flexural properties, a flexural test was carried out inthe following conditions in accordance with ASTM D-790 to determine theflexural modulus.

<Test Conditions>

-   Test specimen: 6.4 mm (thickness)×12.7 mm (width)×127 mm (length)-   Spun distance: 100 mm-   Bending rate: 2 mm/min-   Measuring temperature: 23° C.    Izod Impact Strength

With respect to Izod impact strength, an impact test was carried out inthe following conditions in accordance with ASTM D-256.

<Test Conditions>

-   Test specimen: 12.7 mm (width)×6.4 mm (thickness)×64 mm (length)-   Notch: machining-   Measuring temperature: 23° C.    Gloss

The gloss was determined at an angel of incidence of 60° and angle ofdetection of 60° in accordance with ASTM D523

The specimen for the flow mark observation and ASTM test was injectionmolded in the following conditions.

<Injection Molding Conditions>

-   Resin temperature: 230° C.-   Mold temperature: 40° C.-   Injection time: 5 sec-   Pressure holding time: 5 sec-   Cooling time: 25 sec

Example 2d

To a 20 L internal volume autoclave thoroughly purged with nitrogen, 5Kg of propylene and 3 L of hydrogen were fed and the catalyst suspensionused in Example 1d was added, and bulk homopolymerization was carriedout at 70° C. under a pressure of from 3.0 to 3.5 Mpa for 40 min. Aftercompletion of the homopolymerization, the vent valve was opened and theunreacted propylene was vented until the pressure inside thepolymerization reactor was to atmospheric pressure. After completion ofthe pressure release, in succession, copolymerization of ethylene andpropylene was carried out. That is, an ethylene/propylene mixed gas(ethylene 25 mol %, propylene 75 mol %) was continuously fed andpolymerization was carried out at 70° C. for 60 min, while the openingof the vent valve of the polymerization reactor was regulated so thatthe pressure of the polymerization reactor was 1 Mpa. Adding a smallamount of methanol, the polymerization was stopped and unreacted gas inthe polymerization reactor was purged. The yield of the polyolefin resincomposition (ii) thus prepared was 2.9 Kg. The propylene polymer part(PP-C-ii) in the composition was in an amount of 2.10 Kg, and had a MFR(ASTM D 1238, 230° C., 2.16 Kg load) of 42 g/10 min, a melting point(Tm) of 158° C., a weight average molecular weight (Mw) of 140,000, annumber average molecular weight (Mn) of 70,000 and a Mw/Mn ratio of 2.0.Further, concerning to stereo-regularity of the propylene homopolymerpart (PP-C-ii), the polymer part had a mmmm fraction of 95.7%, and2,1-insertion and 1,3-insertion were not detected. The elastomer (EL-ii)in the composition was in an amount of 0.70 Kg, and had an intrinsicviscosity [η], as measured in decalin at 135° C., of 2.3 dl/g, and anethylene content of 78 mol %. The elastomer (EL-ii) had a weight averagemolecular weight (Mw) of 200,000, an number average molecular weight(Mn) of 90,000 and a Mw/Mn ratio of 2.2. Further, 2,1-insertion based onpropylene monomer was not detected.

The determinations of the amount, composition, molecular weight andstereo-regularity of the polymers prepared in each steps were carriedout in the following manner. Firstly, the polyolefin resin composition(ii) was heat-treated with n-decane at 150° C. for 2 hr, and cooled toroom temperature. Thereafter, the solid component precipitated wasfiltered. The resulting solid component was taken as the propylenepolymer part (PP-C-ii). Further, the filtrate was concentrated and driedunder reduced pressure to prepare a solid component. The solid componentwas taken as the elastomer (EL-ii). With regard to each of thecomponents, various analyses were carried out according to conventionalmethods.

Production of Polyolefin Resin Composition (II)

The polyolefin resin composition (ii) thus prepared, an inorganic filler(C-ii) [talc, manufactured by Hayashi Chemical Co., Ltd, K-1 (TradeMark), average particle diameter 2 μm], Irganox 1010 (Trade Mark)[antioxidant manufactured by Ciba Geigy], Irgafos 168 (Trade Mark)[antioxidant manufactured by Ciba Geigy], ADK-STAB LA-52 (Trade Mark)[hindered amine type light stabilizer, molecular weight=847 manufacturedby Asahi Denka Co., Ltd] and calcium stearate were mixed in theproportion as shown in Table 1d by a tumbler mixer, and thereaftermelt-kneaded by a twin-screw extruder and thereby pelletized.

The polyolefin resin composition (II) thus prepared was injection moldedusing a injection molding machine [manufactured by Niigata Iron WorksCo., Ltd, AN100] into a flat plate (100 mm×300 mm×3 mm thick) and flowmarks were observed. Further, using a injection molding machine(manufactured by Toshiba Machine Co., Ltd, IS100), an ASTM specimen wasinjection molded and the various physical properties thereof weremeasured. The results are shown in Table 1d.

Comparative Example 1d

The procedure of Example 1d was repeated except that as a metallocenecompound, 70 mg of dimethylsilylenebis(2-methyl-4-phenylindenyl)zirconium dichloride was used, and thereby1.99 Kg of a propylene polymer part (PP-C-iii) and 0.66 Kg of anelastomer (EL-iii) were obtained.

The propylene polymer part (PP-C-iii) thus prepared had, a MFR (ASTM D1238, 230° C., 2.16 Kg load) of 40 g/10 min, a melting point (Tm) of150° C., a weight average molecular weight (Mw) of 141,000, an numberaverage molecular weight (Mn) of 60,000 and a Mw/Mn ratio of 2.3.Further, concerning to stereo-regularity of the propylene homopolymerpart, the polymer part had a mmmm fraction of 95.9%, and the proportionof 2,1-insertion was 0.80% and the proportion of 1,3-insertion was0.05%.

The elastomer (EL-iii) thus prepared had an intrinsic viscosity [η], asmeasured in decalin at 135° C., of 2.3 dl/g, and an ethylene content of55 mol %. The elastomer (EL-iii) had a weight average molecular weight(Mw) of 203,000, an number average molecular weight (Mn) of 97,000 and aMw/Mn ratio of 2.1. Further, the proportion of 2,1-insertion based onpropylene monomer was 1.1%.

Production of Polyolefin Resin Composition (III)

The procedure of Example 1d was repeated except for using the propylelepolymer part (PP-C-iii) and the elastomer (EL-iii), to prepare apolyolefin resin composition (III).

The physical properties of the polyolefin resin composition (III) thusprepared were evaluated. The results are shown in Table 1d.

Comparative Example 2d

A commercially available propylene/ethylene block copolymer prepared byusing a magnesium chloride supported titanium catalyst (Ziegler-Nattacatalyst) [Trade Name J708 Grand Polymer Co., Ltd.,] had the followingphysical properties.

The propylene homopolymer part of the propylene/ethylene block copolymerhad a melting point (Tm) of 160° C., a MFR (ASTM D 1238, 230° C., 2.16Kg load) of 40 g/10 min, a Mw/Mn ratio of 4.4 and a decane solublecomponent amount of 11.5 wt %. The n-decane soluble component had anintrinsic viscosity [η], as measured in decalin at 135° C., of 2.8 dl/g.In the decane insoluble component, with regard to the stereo-regularityof the polymer, the mmmm fraction was 96.5% and 2,1-insertion and1,3-insertion were not detected.

Using the propylene block copolymer, a polyolefin resin composition wasproduced in the same procedure as Example 1d. The physical propertiesthereof were evaluated. The results are shown in Table 1d.

TABLE 1d Example Compara. Ex. 1d 2d 1d Polyolefin resin composition(CC-3) [I] [II] [III] 2d <Composition> Propylene polymer (PP-C) wt % 6158 60 71 Elastomer wt % 19 22 20 9 Inorganic filler [Talc] wt % 20 20 2020 Irganox 1010 phr 0.1 0.1 0.1 0.1 Irgafos 168 phr 0.1 0.1 0.1 0.1Calcium stearate phr 0.1 0.1 0.1 0.1 ADK-STAB LA-52 phr 0.1 0.1 0.1 0.1Results of property evaluation Melt flow rate g/10 min 38 41 40 40Tensile elongation % >500 >500 >500 >500 Flexual modulus Mpa 1680 16201700 2000 Izod impact strength (23° C.) J/m 55 58 58 40 Flow marksObservation A A C B-C Gloss % 84 85 75 78 Note 1: When flow marks werenot observed, the molded article was indicated by A. When flow markswere slightly observed, the molded article was indicated by B.

When flow marks were significantly observed, the molded article wasindicated by C.

Note 2: The unit of additive (phr) was based on the total amount of thepropylene polymer, the elastomer and the inorganic filler.

Examples of the propylene elastomers (PBER) are described below.

[Tensile Test]

1. Modulus in Tension:

The modulus in tension was measured in accordance with JIS K6301, usinga JIS No.3 dumbell, at a spun distance of 30 mm, a tensile rate of 30mm/min at 23° C.

[Haze (%)]

The haze was measured using a 1 mm thick specimen by means of a digitalturbidity meter [NDH-20D] manufactured by Nippon Denshoku Kogyo Co.,Ltd.

[Melting Point (Tm) and Glass Transition Temperature (Tg)]

The endothermic curve of DSC was determined and the temperature at themost peak position was taken as Tm.

In the measurement, a specimen was packed in an aluminum pan, heated to200° C. at an elevating rate of 100° C./min, and kept at 200° C. for 5min. Thereafter the specimen was cooled to −150° C. at a cooling rate of10° C./min and then heated at an elevating rate of 10° C./min. In thetemperature elevating, the temperature was determined from theendothermic curve. In measuring DSC, from the endothermic peak, theamount of heat of fusion per unit weight was determined, and then theamount was divided by the amount of heat of fusion of polyethylenecrystal 70 cal/g to determine a crystallinity (%).

[Intrinsic Viscosity [η]]

The intrinsic viscosity was measured in decalin at 135° C.

[Mw/Mn]

The Mw/Mn ratio was measured using a GPC (Gel permeation chromatography)with ortho-dichloro benzene solvent at 140° C.

Example 1e Synthesis of Propylene Elastomer (PBER) (HereinafterOccasionally Referred to as Propylene/Ethylene/Butene Copolymer)

To a 2000 ml polymerization reactor thoroughly purged with nitrogen, 833ml of dried hexane, 100 g of 1-butene and triisobutyl aluminum (1.0mmol) were fed at room temperature. Thereafter, the internal temperatureof the polymerization reactor was elevated to 40° C., the pressure inthe system was set to 0.76 Mpa by pressurization with propylene and thepressure in the system was regulated to 0.8 Mpa with ethylene.Subsequently, a toluene solution prepared by allowing 0.001 mmol ofdimethylmethylene(3-tert-butyl-5-methylcyclopentadienyl)fluorenylzirconium dichloride to contact with 0.3 mmol, in terms of aluminum, ofmethyl aluminoxane (manufactured by Tosoh Finechem Corporation) wasadded to the polymerization reactor and polymerized for 20 min while theinternal temperature was kept to 40° C. and the system pressure was keptto 0.8 Mpa with ethylene. Adding 20 ml of methanol, the polymerizationwas stopped. The pressure was released, and then a polymer wasprecipitated from the polymerization solution in 2 L of methanol anddried at 130° C. in vacuo for 12 hr. The polymer was obtained in anamount of 46.4 g and had an intrinsic viscosity [η] of 1.81 dl/g. Thephysical properties of the resulting polymer were measured and wereshown in Table 1e.

Example 2e Synthesis of Propylene/Ethylene/butene Copolymer

To a 2000 ml polymerization reactor thoroughly purged with nitrogen, 883ml of dried hexane, 70 g of 1-butene and triisobutyl aluminum (1.0 mmol)were fed at room temperature. Thereafter, the internal temperature ofthe polymerization reactor was elevated to 40° C., the pressure in thesystem was set to 0.76 Mpa by pressurization with propylene and thepressure in the system was regulated to 0.8 Mpa with ethylene.Subsequently, a toluene solution prepared by allowing 0.001 mmol ofdimethylmethylene(3-tert-butyl-5-methylcyclopentadienyl)fluorenylzirconium dichloride to contact with 0.3 mmol in terms of aluminum ofmethyl aluminoxane (manufactured by Tosoh Finechem Corporation) wasadded to the polymerization reactor and polymerized for 30 min while theinternal temperature was kept to 40° C. and the system pressure was keptto 0.8 Mpa with ethylene. Adding 20 ml of methanol, the polymerizationwas stopped. The pressure was released, and then a polymer wasprecipitated from the polymerization solution in 2 L of methanol anddried at 130° C. in vacuo for 12 hr. The polymer was obtained in anamount of 53.1 g and had an intrinsic viscosity [η] of 1.82 dl/g. Thephysical properties of the resulting polymer were measured and wereshown in Table 1e.

Example 3e Synthesis of Propylene/Ethylene/butene Copolymer

To a 2000 ml polymerization reactor thoroughly purged with nitrogen, 917ml of dried hexane, 50 g of 1-butene and triisobutyl aluminum (1.0 mmol)were fed at room temperature. Thereafter, the internal temperature ofthe polymerizer was elevated to 70° C., the pressure in the system wasset to 0.76 Mpa by pressurization with propylene and the pressure in thesystem was regulated to 0.78 Mpa with ethylene. Subsequently, a toluenesolution prepared by allowing 0.002 mmol ofdiphenylmethylene(3-tert-butyl-5-methylcyclopentadienyl)(2,7-di-tert-butyl-fluorenyl)zirconiumdichloride to contact with 0.6 mmol in terms of aluminum of methylaluminoxane (manufactured by Tosoh Finechem Corporation) was added tothe polymerization reactor and polymerized for 30 min while the internaltemperature was kept to 70° C. and the system pressure was kept to 0.78Mpa with ethylene. Adding 20 ml of methanol, the polymerization wasstopped. The pressure was released, and then a polymer was precipitatedfrom the polymerization solution in 2 L of methanol and dried at 130° C.in vacuo for 12 hr. The polymer was obtained in an amount of 67.6 g andhad an intrinsic viscosity [η] of 1.42 dl/g. The physical properties ofthe resulting polymer were measured and were shown in Table 1e.

Example 4e Synthesis of Propylene/Ethylene/butene Copolymer

To a 2000 ml polymerization reactor thoroughly purged with nitrogen, 859ml of dried hexane, 85 g of 1-butene and triisobutyl aluminum (1.0 mmol)were fed at room temperature. Thereafter, the internal temperature ofthe polymerization reactor was elevated to 65° C., the pressure in thesystem was set to 0.76 Mpa by pressurization with propylene and thepressure in the system was regulated to 0.77 Mpa with ethylene.Subsequently, a toluene solution prepared by allowing 0.002 mmol ofdiphenylmethylene(3-tert-butyl-5-methylcyclopentadienyl)(2,7-di-tert-butyl-fluorenyl)zirconiumdichloride to contact with 0.6 mmol in terms of aluminum of methylaluminoxane (manufactured by Tosoh Finechem Corporation) was added tothe polymerization reactor and polymerized for 30 min while the internaltemperature was kept to 65° C. and the system pressure was kept to 0.77Mpa with ethylene. Adding 20 ml of methanol, the polymerization wasstopped. The pressure was released, and then a polymer was precipitatedfrom the polymerization solution in 2 L of methanol and dried at 130° C.in vacuo for 12 hr. The polymer was obtained in an amount of 67.6 g andhad an intrinsic viscosity [η] of 1.42 dl/g. The physical properties ofthe resulting polymer were measured and were shown in Table 1e.

Comparative Example 1e Synthesis of CrystallinePropylene/Ethylene/butene Copolymer

To a 1.5 L autoclave which had been dried under reduced pressure andpurged with nitrogen, 675 ml of heptane was fed at room temperature.Subsequently, a 1.0 mmol/ml toluene solution of triisobutyl aluminum(hereinafter abbreviated as TIBA) was added in an amount of 0.3 ml i.e.,in terms of aluminum atom of 0.3 mmol to the autoclave and then 28.5 L(25° C., 1 atm) of propylene and 10 L (25° C., 1 atm) of 1-butene werefed with stirring, and the temperature was elevated to 60° C.Thereafter, the internal system was pressurized to be 6.0 Kg/cm²G withethylene, and 7.5 ml of a toluene solution (0.0001 mM/ml) ofrac-dimethylsilylene-bis(2-methyl-4-phenyl-1-indenyl)zirconiumdichloride and 2.3 ml of a toluene solution (0.001 mM/ml) oftriphenylcarbenium tetra(pentafluorophenyl)borate, which weresynthesized in the conventionally known methods were added to startcopolymerization of propylene, ethylene and 1-butene. In thecopolymerization, based on the overall system, the catalystconcentration ofrac-dimethylsilylene-bis(2-methyl-4-phenyl-1-indenyl)zirconiumdichloride was 0.001 mmol/L and that of triphenylcarbeniumtetra(pentafluoro-phenyl)borate was 0.003 mmol/L.

During the polymerization, ethylene was continuously fed and thereby theinternal pressure was kept to 6.0 Kg/cm²G. After 15 min from thebeginning of polymerization, the polymerization was stopped by addingmethyl alcohol. The pressure was released and a polymer solution wastaken out and washed with an aqueous solution prepared by adding 5 ml ofconcentrated hydrochloric acid to 1 L of water, in such an amount thatthe proportion of the polymer solution and the aqueous solution was 1:1.The catalyst residue was transferred to a water phase. The catalystmixed solution was allowed to stand and the water phase was removed byseparation. Further, the remainder was washed with distilled water twiceto separate the polymerization liquid phase into oil and water. Next,the polymerization liquid phase was allowed to contact with 3 times theamount of acetone with vigorous stirring to precipitate a polymer.Thereafter, the polymer was sufficiently washed with acetone and thesolid part (copolymer) was collected by filtration. The copolymer wasdried in a stream of nitrogen at 130° C. at 350 mmHg for 12 hr. Thepropylene/butene/ethylene copolymer was obtained in a yield of 24 g andhad an intrinsic viscosity [η] as measured in decalin at 135° C. of 1.9dl/g. The physical properties of the resulting polymer were measured andwere shown in Table 1e.

TABLE 1e Com. Item Ex. 1e Ex. 2e Ex. 3e Ex. 4e Ex. 1e Propyleneelastomer [PBER] (Isotactic propylene/ ethylene/butene copolymer) C2(mol %) 17 13 18 10 10 C4 (mol %) 9 7 10 17 15 C3/C2 (molar ratio) 81/1986/14 80/20 88/12 88/12 [η] (dl/g) 1.81 1.82 1.42 1.78 1.9 Tm (° C.) NotNot Not Not Not observed observed observed observed observed Tg (° C.)−27.6 −26.9 −29.3 −23.9 −25.1 Mw/Mn 2.2 2.1 2.2 2.1 2.4 Modulus intension 2 10 7 10 42 (YM) (Mpa) Transparency (Haze) (%) 5 5 7 9 19

INDUSTRIAL APPLICABILITY

The sheets and films prepared by the polypropylene compositions (CC-2,CC-3) containing the propylene/1-butene random copolymer and thepropylene/1-butene random copolymer according to the present inventionhave excellent balance of transparency, flexibility and heat-sealproperties. Further, the stretched films therefrom have excellentshrinking properties. Therefore, they are suitable for use as sheets orfilms for packaging food and the like.

The sheets and films prepared by the polypropylene compositions (CC-2,CC-3) containing the propylene/1-butene random copolymer and thepropylene/1-butene random copolymer according to the present inventionhave excellent transparency, flexibility, blocking resistance andheat-seal properties. Particularly, they can be heat-sealed even at lowtemperatures so that they can be heat-sealed in a wide temperaturerange, and further have excellent heat-seal strength. Additionally evenafter long-term storage, the heat-seal temperature thereof is notchanged with time and the stable heat-sealability is secured. Thestretched films obtainable by stretching the above sheets or films haveexcellent heat-seal properties, blocking properties and shrinkingproperties.

The sheets, films and stretched films according to the presentinvention, further, have excellent transparency, scratching resistanceand blocking resistance and can perform high-speed packaging. Therefore,they are suitably used for food packaging, packed wrapping, fiberpackaging and other uses.

The transition metal compound having ligand such that a cyclopentadienylgroup having substituent groups at two positions not adjacent each otherand a fluorenyl group are bridged with a carbon atom substituted with anaryl group according to the present invention are novel and useful as anolefin polymerization catalyst component.

The use of the olefin polymerization catalyst containing the transitionmetal compound can give a process for producing an olefin copolymerhaving a high molecular weight.

The polyolefin resin composition (CC-3) of the present inventioncontains a specific propylene polymer (PP-C) and a specific elastomer(EL) in a specific proportion so that it can prepare molded products(including injection molded products) having excellent balance intensile strength, flexural modulus and impact resistance and excellentmechanical strength, high gloss and good appearance such that flow marksare hardly induced, or even if induced, flow marks are not prominent.

The polyolefin resin compositions of the present invention are suitablyused in preparing various molded products typically in injection moldedproducts by making use of the above properties.

1. A transition metal compound represented by the following formula(2a):

wherein each of R¹ and R³ is hydrogen, R² and R⁴ are the same ordifferent from each other and selected from the group consisting of ahydrocarbon group and a silicon-containing group, R⁵, R⁶, R⁷, R⁸, R⁹,R¹⁰, R¹¹, R¹² and R¹³ are the same or different from each other andselected from the group consisting of a hydrogen, a hydrocarbon groupand a silicon-containing group, and adjacent substituent groups R⁵ toR¹² are optionally linked to form a ring, R¹⁴ is an aryl group, and R¹³and R¹⁴ are the same or different from each other and optionally linkedto form a ring; M is a Group 4 transition metal; Y is a carbon atom; Qis identical or different from each other and selected from the groupconsisting of halogen, a hydrocarbon group, anion ligand or neutralligand capable of coordination with a lone pair of electrons; and j isan integer of 1 to
 4. 2. The transition metal compound according toclaim 1, wherein each of R¹³ and R¹⁴ in the formula (2a) issimultaneously an aryl group.